Novel and highly cost effective technology for capture of industrial   emissions without reagent for clean energy and clean environment  applications

ABSTRACT

In this patent we disclose, for the first time, detailed methods of our newly invented state-of-the-art cryogenic technology for the cost effective energy efficient capture of each known component of entire emissions (nearly 100%) such as carbon dioxide (CO 2 ), sulfur oxides (SO x ), nitrogen oxides (NO x ), carbon monoxide(CO), any other acid vapor, mercury, steam and unreacted nitrogen from industrial plants (coal and natural gas fired power plants, cement plants etc.), in a liquefied or frozen/solidified form, such that each of the components is captured separately and is industrially useful. This new technology includes a novel NH 3  power plant to generate auxiliary electrical power from the heat energy of the flue gas to further improve the energy efficiency and cost effectiveness of the capture processes. It is the most cost effective of all existing emission capture technologies. It does not require use of any chemicals/reagents/external cryogens, unlike the current technologies. It uses only a fixed amount of water needed for the cooling process which can be used repeatedly. We present detailed methods of operations, together with scientific and economic analysis of the energy needed and cost involved for the said capture in two specific examples, and advantages of the new technology over the existing ones.

In this patent we disclose, for the first time, detailed methods of ournewly invented state-of-the-art cryogenic technology for the costeffective energy efficient capture of each known component of entireemissions (nearly 100%) such as carbon dioxide (CO₂), sulfur oxides(SO_(x)), nitrogen oxides (NO_(x)), carbon monoxide(CO), any other acidvapor, mercury, steam and unreacted nitrogen from industrial plants(coal and natural gas fired power plants, cement plants etc.), in aliquefied or frozen/solidified form, such that each of the components iscaptured separately and is industrially useful. This new technologyincludes a novel NH₃ power plant to generate auxiliary electrical powerfrom the heat energy of the flue gas to further improve the energyefficiency and cost effectiveness of the capture processes. It is themost cost effective of all existing emission capture technologies. Itdoes not require use of any chemicals/reagents/external cryogens, unlikethe current technologies. It uses only a fixed amount of water neededfor the cooling process which can be used repeatedly. We presentdetailed methods of operations, together with scientific and economicanalysis of the energy needed and cost involved for the said capture intwo specific examples, and advantages of the new technology over theexisting ones.

FIELD OF INVENTION

This invention relates to the cost effective and energy efficientcapture of components of emissions (toxic acid gases, mercury, CO₂, CO,unreacted nitrogen) contained in the flue gases from power plants andindustries in general, without the use of any chemical/reagent (exceptwater) [after removal of fly ashes and mercury oxides]. This newtechnology is based on (i) the fractional condensation of each componentgas at appropriate temperature through compression, cooling withsuper-cold nitrogen (of the flue gas) obtained at the end of the cycleand isentropic expansion; (ii) generation of auxiliary power from theheat of the flue gas to make the process energy efficient and furthercost effective; (iii) scientific analysis of application of thistechnology to two specific cases of power generation using coal andnatural gas. More particularly, this invention relates to theapplications for clean energy generations in coal and natural gas powerplants and for clean environment for this purpose.

BACKGROUND OF THE INVENTION

Electric power plants and cement factories release flue gas thatcontains large amount of pollutants (carbon dioxide (CO₂, NO_(x)(Nitrogen oxides), (x=0.5,1,1.5,2,2.5), SO_(x) (sulfur oxides), (x=2,3),mercury (Hg) and its oxides, volatile organic compounds(VOCs), soot andparticulate matters (PM) along with hot steam and unreacted nitrogen tothe atmosphere. The pollutants (except steam and nitrogen) causeenvironmental pollution and contribute to global warming. Literaturesabound on the nature, amount, the effects on health and environment ofthese emissions, the current state-of-the-art technologies for capturingthese emissions, the cost implications to control the emissions in partor full. By studying a number of such literatures [Refs. 1-79, Refs.T1-T5, Refs Z1-Z4, we find that:

-   -   (i) There is no single technology that can remove/capture, with        one installed equipment, mercury and its oxides, sulfur oxides,        nitrogen oxides, acid vapors in general, carbon dioxide, carbon        monoxide from flue gas of coal power plants and industrial        plants in general;    -   (ii) The cost of installation of the different equipment needed        for removal/capture of individual component is too high for many        countries in the world to afford and even in the USA not all        plants can easily be retrofitted with existing clean energy (or        full emission capture) equipment, because of high installation        and operational costs involved (which can be seen in the cited        literature);    -   (iii) The cryogenic techniques [63,64,62p,65,66]] investigated        so far have been found to be very energy intensive and have not        so far addressed the techniques of separation of various        individual toxic component of the flue gas and has mostly        focused on separation of CO₂ at costs much higher than the        state-of-the art amine technology employed for capture of CO₂.        These are found to be not commercially viable for large scale        capture of CO₂ and capture of other individual components of        flue gas.    -   (iv) The cost of CO₂ capture with current state-of-the-art amine        technologies of CO₂ capture is still very high [62,62a-c, 12a,        72-79]. The storage and retrieval of the gaseous CO₂ is quite        tedious apart from huge cost involved, as it requires        transportation of the captured CO₂ to empty oil or coal fields        underground.    -   (v) Environmental pollution from such plants [1-42] is        increasing globally and global warming is becoming a threat for        humanity, specially, when demands & usage for and uses of fossil        fuel power continues to increase globally.    -   (vi) Thus, there is a need to develop a new technology which is        very cost effective and energy efficient so that one installed        equipment can capture/remove all (nearly 100%) the toxic        components like SO_(x), NOR, Hg, CO and CO₂ from coal power and        other industrial plants such that the removed components can        find industrial uses and the cost effective technology/equipment        can be employed even in countries which currently do not employ        any emission capture technology. Moreover, the new technology        would be such that it allows capture of these items in a form or        forms that can easily be stored and retrieved when needed for        uses. This is where our new emission capture invention excels        over all existing state-of-the-art emission capture technologies        that can be retrofitted to industrial plants but at very high        costs. The new technology is very cost effective with very low        operational costs as it does not require any reagent/chemical        agent and requires significantly lower energy per ton of        pollutant capture than any existing technology. Moreover, our        new technology captures the above items in forms that are very        easy to store and each component separately.

OBJECTS OF THE INVENTION

Therefore, an object of the invention is to provide a new cryogenictechnique that can capture each component of the gaseous emissions (fluegas) from power plants, cement plants and industries in general withoutthe use of any chemical agent or reagent (except fixed amount of water)and with minimum energy usage, high efficiencies and at low cost notheretofore possible. Still another object is to provide a method ofseparating and capturing each component of the flue gas [mercury, steam,SO₃ (sulfur trioxide), SO₂ (sulfur dioxide), N₂O (nitrous oxide), NO(nitric oxide), NO₂ (nitrogen dioxide), CO₂ (carbon dioxide), CO (carbonmonoxide), unreacted nitrogen] from power plants individually in pureform (such that each captured component itself is industrially useful)with one single equipment which is much easier to apply and whichproduces results, not possible by any technology before. Another objectis to capture the heat of the flue gas for production of auxiliary powerin an efficient way so as to improve the cost effectiveness and energyefficiency of the whole capture processes further. A final object is toprovide an improved apparatus/equipment capable of employing cryogenictechnique with auxiliary power generation from the flue gas heat and useof super cooled nitrogen gas produced at the end of the cycle to captureeach said component of the flue gas emission from industries in generalin most cost effective and energy efficient way, and in forms such thatthe captured components find industrial applications and can easily bestored.

SUMMARY OF THE INVENTION

This invention is a process by which emission gasses from power plantsand industries in general are fractionally condensed using a series ofheat exchangers, compressors and expansion valves, to separate, captureand store the constituents (oxides of sulfur and nitrogen, mercury (Hg),carbon monoxide (CO) and most importantly, carbon dioxide (CO₂)) usingno chemical/reagent but lowest amount of electrical energy and a fixedamount of water (the fixed amount of water can be repeatedly used). Thepower required for this is augmented with an ammonia power plant forvery high energy efficiency and relatively very low cost.

The objects stated above are attained using methods that includecryogenic technique for capture of individual component of an industrialflue gas comprising the steps of:

-   -   (a) Capture of the heat of flue gas from the power plants and        industrial plants in general for the generation of auxiliary        power using anhydrous ammonia turbine.    -   (b) Separation of ashes, soot, mercury oxides etc. from the said        flue gas by first using ceramic filters, conventional fabric        filter and electrostatic separation similar to conventional        technologies.    -   (c) Capture of partial SO₃ and partial mercury through heat        exchange in the process of said turbine expansion (step (a)).    -   (d) Capture of SO₃, mercury and steam of the flue gas through        compression and cooling in a specially designed coil immersed in        a specially designed water tank which is cooled by passing cold        nitrogen gas (of the said flue gas) obtained at the end of the        cycle through tubes immersed in water and by using radiative        heat exchange, if and when necessary (depending on the        temperature of the flue gas after the auxiliary power        generation) so that a fixed amount of water is maintained at a        specified temperature for this capture.    -   (e) Capture of NO₂ and remaining steam of the said flue gas        through compression and cooling of the said flue gas in the said        similar coiled tubes and tank at specified temperature.    -   (f) Capture of SO₂ of the said flue gas by further compression        from step (e) and cooling in a special tank containing heat        conducting blackened pebbles or metal chips and helium gas, the        tank being cooled at a specified temperature by flowing cold        nitrogen gas obtained at the end of the operation.    -   (g) Capture of CO₂ of the flue gas in the form of cold liquid        CO₂ (LCO₂) after step (f) by further compression and cooling in        another said similar special tank.    -   (h) Conversion to dry ice by throttling said LCO₂ of step (g) in        a flash chamber, freezing the dry ice and the dry CO₂ vapor with        part of said cold nitrogen gas and cooling the remaining flue        gas (after operation g) by flowing (passing) part said super        cooled N₂ gas obtained at the end of cycle into the said        chamber.    -   (i) Further cooling of the flue gas of step (h) containing        mostly N₂ and small percentage of NO, N₂O and CO by the cold N₂        gas exiting the said chamber.    -   (j) By first, second and third stage of isentropic turbine        expansion of the compressed flue gas remaining after step (i) to        condense, N₂O, NO and finally CO separately into appropriate        chambers (tanks) cooled by flow of super cooled N₂ obtained at        the end of the cycle following capture of CO.    -   (k) Using the turbine expansion work at step (j) of compressed        flue gas to drive some of the shafts of earlier compressors.    -   (l) Using the super-cooled N₂ gas (of the flue gas) obtained        at (j) to cool the flue gas at earlier stages of operation as        mentioned in (a) to (k).

The methods associated with steps (a) to (l) ensure:

-   -   Capture of CO₂, SO_(x), NO_(x), CO and mercury contained in the        flue gas from coal and natural gas fired power plants and        industries in general, at costs much lower than any existing        current technology could allow.    -   The most cost effective and energy efficient means of capturing        large volumes of CO₂ of the flue gas from power plants and        industrial plants in general and conversion to cold liquefied        pure CO₂ and dry ice, which are sources of highly pure CO₂ and        which can find large industrial applications currently and in        future.    -   The most cost effective and energy efficient means of obtaining        pure N₂ gas from the flue gas of power plants.    -   The most cost effective means of mitigating global warming and        environmental pollution arising out of the flue gas from power        plants and industries in general.

The above methods are supported by scientific analysis of the energyrequirement for capture and liquefaction of CO₂ and super cooling ofunreacted nitrogen gas of the flue gas, using data in two specificexamples of power generation. Detailed methods of scientific analysis ofthe net energy requirement and the cost involved in two specificexamples for the steps g through l (which are described in details insection I) are included in this invention. The estimated cost of captureCO₂ in liquefied and or frozen form includes cost of capture of thetoxic components also, the largest part of the flue gas from mostfossil-fuel combustion is uncombusted nitrogen [(1) Perry, R. H. andGreen, D. W. (Editors) (1997). Perry's Chemical Engineers' Handbook (7thed.). McGraw Hill. ISBN 0-07-049841-5; (2) Rogers and Mayhew(1992)[80]].

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a block diagram which shows schematically the main equipmentin accordance with the invention for capturing each component of fluegas emissions from power and industrial plants separately. It comprisesof: (i) NH₃ super heater with ceramic filters; (ii) precipitator/fabricfilter; (iii) heat exchangers (some for temperatures above 0° C. andothers for temperatures below 0° C. up to slightly above liquidnitrogen); (iv) NH₃ turbine with condenser & pump; (v) partial H₂O andHg collection chamber; (vi) N-stage compressors with water coolingarrangement using heat exchangers for complete H₂O/SO₃/Hg collection;(vii) sections for productions & collections of liquefied NO₂, SO₂, CO₂,and N₂O including arrangement for appropriate heat exchangers; (viii)sections for production and collection of dry ice from liquefied CO₂;(ix) triple stage N₂ turbine expanders for cooling N₂ gas of the fluegas; (ix) NO & CO collection chambers.

FIG. 2 is the temperature-entropy (T-S) diagram of carbon dioxide duringproduction of liquefied CO₂ and dry ice from the flue gas during steps12 to 14 in section I.1 of STEPS & PROCESSES INVOLVED TO ACHIEVE THESAID OBJECTS OF INVENTION.

FIG. 3 is a temperature—entropy (T-S) diagram of a super criticalanhydrous NH₃ power plant used to generate auxiliary power by capturingthe heat of the flue gas.

FIG. 4 is cross sectional view of the ceramic plates used to captureashes of the flue gas. The separation of the holes being the same as thediameter (d) of the holes and the distance between the rows of holes isseparated by about 3d.

FIG. 5 is an arrangement of the ceramic filters in two chambers tocapture ashes and the position of ammonia super heater.

FIG. 6 is a sectional view of the special tubes for condensation ofmercury, steam, SO₃ and other components of flue gas with boiling pointabove 0° C.; These special tubes are to be kept inside the heatexchanger (FIG. 11) after fabric filter or before the N-stage compressorin FIG. 1. The arrangement prevents escape of the flue gas duringcondensation and collection of components.

FIG. 7 is a sectional view of specialized tubes ABCDE inside a specialwell insulated chamber to condense each component of flue gasesseparately. The equipment is used several times in the capture processesdescribed in this invention. Its design depends on the nature ofcaptured items as follows: A. For collection of steam, SO₃, Hg, HCl, NO₂the tubes are immersed in water inside the chamber and the water iscooled by controlled amount of cold nitrogen gas passing through manyturns of heat conducting tubes (not shown in FIG. 7) connecting portX₁X₂ with port Y₁Y₂. B. For collection of liquefied SO₂, CO₂, N₂O, NO,CO, each separately, the chamber does not contain any water and any ofthe following arrangement is made. (i) The chamber contains the extratubes of part A and no water. For capture of components with boilingpoint below 0° C., the chamber is filled with helium gas at pressure 1to 2 bar in sealed (air tight) condition for capture of components withboiling point below 0° C. (ii) Instead of water, the chamber containsheat conducting pebbles or metal chips arranged on perforated rackshorizontally placed (not shown in FIG. 7) such that the rack surroundthe turns of tubes carrying cold (or super cold, as needed) nitrogengas. The latter surrounds the turns of tubes carrying flue gas. Whilethe conducting pebbles help retain the low temperature produced by thecold nitrogen, the helium gas speedily conducts away the heat from thesurface of the flue gas tubes to the cold conducting pebbles and thetubes carrying the cold nitrogen. The cold nitrogen gas (obtained fromthe flue gas at the end of the cycle) enters through tube X₁X₂ passesthrough the said turns of heat conducting tubes connecting X₁X₂ andY₁Y₂, inside the chamber; it finally exits through Y₁Y₂. In all thearrangements, the cold N₂ gas exits out through Y₁Y₂ to enter anothersimilar cooling chamber. For any of the arrangement, A or B, the chamberis air tight and water leak proof when water is used. Arrangements (i) &(ii) are preferred if very pure nitrogen gas is to be collected at theexit point near a-b₁ in FIG. 1. With arrangement (i) helium gas enablesrapid heat exchange between flue gas and the cold nitrogen gas throughtubes connecting X₁ X₂ with port Y₁ Y₂. The heat exchange can be furtherenhanced by using a small fan (not shown in FIG. 7) that will circulatethe helium gas throughout the chamber, and thereby increasing the heatexchange rate. For good insulation, the inner walls of the chamber arecoated with reflecting materials and the outside walls containsalternate layers of shining aluminum sheets and Styrofoam. This deviceis the heat exchanger referred to many times for capture of flue gascomponents with boiling point temperature below 0° C. in FIG. 1 and inthe descriptions of methods, claims etc. contained in this disclosure ofinvention.

FIG. 8 is a sectional view of another type of specialized coiled tubesthat also can be used to condense and collect liquefied steam, SO₃, Hg,NO₂, SO₂. The spring at the end of the lower tube prevents escape of theflue gases when enough liquid is not formed.

FIG. 9 is a sectional view of a flash chamber for the formation andcollection of dry ice. Very cold N₂ gas, obtained at the end of thecycle, is inserted into the chamber to freeze the remaining dry vapor tosolid dry ice through one port and exited out after freezing the dry CO₂vapor at −78° C. to solid dry ice. The flash chamber contains a throttlevalve which is connected to the insulated chamber collecting liquefiedCO₂ at step 12 in section I.1

FIG. 10 is a sectional view of flash chamber for collection of N₂O, NOand CO.

FIG. 11 Is a sectional view of heat exchanger used to cool (for captureof components having b.pt above 0 C) compressed flue gas at differentsteps in this invention. The heat exchanger contains water which iscooled by controlled reverse flow of cold nitrogen gas obtained at theend of the flue gas process cycle. The cold nitrogen gas enters throughone port of a several turns of heat conducting tubes and exits outthrough a second port. These turns of cold nitrogen carrying tubessurrounds the flue-gas flow tubes of FIG. 6 (not shown in FIG. 11) ofwhich the exit pipe for the condensates passes through the bottom ofwall of this chamber. The water is stirred as needed (the stirrer notshown in FIG. 11).

The flue-gas flow tubes of FIG. 6-8 are made of special materials thatcan stand temperature ˜300° C., possess high thermal conductivity and atthe same time non-corrosive to the toxic components of the flue gas.Such materials are described in section I.1 [under title “_Protection ofequipment from corrosion due to acidic oxides, acid vapors and toxicmaterials in the flue gas during the entire capture process” before step1 of the processes of this invention].

The “reverse direction” of cold nitrogen gas flow as mentioned manytimes in this invention refers to direction from right to left withrespect to the equipment schematically shown in FIG. 1.

SPECIFIC (DETAILED) DESCRIPTION

The Present Invention

Our cost effective and energy efficient technique captures toxiccomponents of the flue gas from power plants and industries in generaland the carbon dioxide in liquefied or frozen form, as needed, withoutthe use of any chemical/reagent. It generates auxiliary power usinganhydrous ammonia to make the processes (of capturing the emissions)further energy efficient and cost effective. The new technique is alsogoing to be especially useful and cost effective to capture the entirecarbon dioxide (a global warming agent), if that is left over aftercontrolling the toxic emissions and the particulates using the existingbut expensive current state-of-the art technologies, which can be seenin the cited literature Refs. 1-79, Refs T1-T5, Refs.Z1-Z4. The currentstate-of-the-art technologies for capture of components of emissions offlue gas require extensive uses of both chemicals, water and power andas a result even in advanced countries many power plants cannot affordto apply them. Our very cost effective technology of invention is usefulto capture any one or all components of emissions from coal/naturalgas/oil fired power plants, generators and emissions from industries,such as cement etc. in general. Thus the technology is useful to preventenvironmental pollution and mitigate climate changes resulting from thepollution.

We discuss below in details the various steps/processes involved in ournew industrial emission capture technique. Our technique will producevast amount of pure liquid CO₂ and dry ice (source of very pure CO₂)from the flue gas of the power plants very cost effectively. In thisinvention, we have used a total of 15 compressors and three turbineexpanders and assessed (through rigorous scientific analysis) the energyefficiency & cost efficiency of the new technology in capturing theentire flue gas emissions in two specific cases: coal power generationand natural gas power generation. However, due to space limitation only5 compressors are shown in FIG. 1. Each compressor block in FIG. 1 maybe assumed to be three small compressors. In FIG. 1, the coldestnitrogen gas (1 to 2° C. above its boiling point −196° C.) is obtainedat the point i(FIG. 1) after the triple stage expansion. It is dividedinto two lines at the point r. One goes to the CO₂ flash chamber and theother to the NO condensation chamber. The arrowed line path indicated bythe points q-j-k-l-m indicates the flow (in reverse direction) of coldnitrogen obtained at the end of triple stage expansion of compressedflue gas (see the steps below). At the point m, the cold nitrogen gasline is again split in two lines as shown in FIG. 1 and explained below.

The steps involved in separately capturing each component of flue gas(emissions) from coal fired and natural gas fired power plants andindustrial plants in general, with this new technology are discussedbelow in reference to FIG. 1 through 11. In this invention wherever“ammonia” is mentioned, it refers to anhydrous ammonia.

In the steps described below we call our invention the new clean energytechnique (NCET).

I.1. Steps/Processes Involved to Achieve the Said Objects of Invention

Protection of Equipment from Corrosion Due to Acidic Oxides, Acid Vaporsand Toxic Materials in the Flue as During the Entire Capture Process

In all steps/processes described below, the equipment surfaces, internaland external surfaces of tubes and surfaces of capture-vessels that comein contact with the acidic oxides, acids that may form on reactions ofthe oxides with condensed steam and other toxic components of the fluegas and or the captured liquefied products of these components, areprotected as follows: they are either coated with or made of any one ofthe following plastics: vespel, torlon, ryton, noryl of craftechindustries[http://www.craftechind.com/dont-sweat-4-high-temp-plastics-can-take-heat/#comment-741]or any material that is non-reactive to these components and at the sametime the material must have very good thermal conductivity and highrange of temperature tolerance.

All of these plastics can tolerate very well temperature around 100° C.Vespel tolerates well temperature up to 300° C. It is used for tubes andvessels at high temperature end of the flue gas processing. These arenon-corrosive to all components of flue gas. Alternately, copper tubeswith inner and outer coating (about 2 mm thick) with any one of thesematerials (plastics) are also found to be suitable in this invention foruse in the methods described to capture the toxic components of the fluegas. This would ensure better heat transfer required for fastcondensation of the components. However, fully plastic tubes are cheaperthan the latter ones. It is extremely important for all components ofthis emission capture plant are coated with non-corrosive, temperatureresistant coating/paint with good thermal conductivity. The ammoniasuper-heater chamber of FIG. 1 and in steps 2 to 5 below is made of suchhigh temperature tolerant and non-corrosive plastic possessing highthermal conductivity. The surface of the chamber is coated with thinlayer of a material with high heat absorptivity (for good absorption ofheat from flue gas) and low heat emissivity (low heat transfer to theflue gas or surrounding). One of such materials is nickel oxide whichhas high absorptivity (0.92) and low emissivity (0.08)[http://www.solarmirror.com/fom/fom-serve/cache/43.htm1]. The tubes inFIG. 7 are also made of such materials.

Capture of Fly Ashes, Soot, Mercury Oxides

STEP 1: The new clean energy technology (NCET) is schematically depictedthrough FIGS. 1-11. The flue gas from the boiler of a power plant [afterboiling the water to high pressure steam that drives the turbine] ispassed through a series of ceramic filter plates(FIG. 4) arranged in twochambers [FIG. 5] to remove the fly ashes that may include mercuryoxides (HgO & Hg₂O) and soot (if coal is used). In the first chamber,each ceramic filter (FIG. 4) is lined with circular holes of a givendiameter (for a given filter) that varies from 5 mm to 1 mm. A ceramicplate has holes of a given diameter arranged as shown (FIG. 4). Thenumber of holes in a line and the number of lines can vary depending onvolume of flue gas to be filtered out. The separation of holes in agiven line is about 2 to 3 times the diameter of one hole. The lines arealso similarly separated. Two plates containing holes of same diameterare placed on top of or next to each other in cross position so that xaxis (the side cd or ab) of one plate becomes the y axis (the side ad orbc) of the other plate [FIG. 4]. The separation between the plates issix to eight inches. There are five such pairs of ceramic plates in onechamber. The diameter of the holes in a given pair of plates decreasesfrom the previous pair by 1 mm. The last pair has holes of diameter 1mm. These chambers are well insulated to prevent heat losses from theflue gas. The ceramic plates are arranged so that they can be cleanedeasily of the ashes/soot/solid HgO and Hg₂O. The chambers are sodesigned that the ashes can be removed from time to time easily. Theflue gas from coal fired power plants is then passed through fabricfilters to remove the remaining ashes/soot. This also can remove some ofthe mercury oxides. These arrangements (not shown in FIG. 1) are madebefore the flue gas enters the ammonia super heater in FIG. 1 and FIG.5. Such arrangement are suitable for flue gas containing high ash,specially, from power plants (e.g., those from India) using coal withhigh ash content. In this invention we find that such arrangements toremove fly ash, mercury oxides is not necessary if the flue gas is fromnatural gas fired power plants.

Capture of Flue as Heat for Auxiliary Power Generation Through Steps 2to 5

Step 2: (After the step/process 1), the flue gas is passed through achamber [FIG. 1] that contains an ammonia super heater [FIG. 1, FIG. 5]which heats (using the heat of the flue gas) the anhydrous ammonia ofthe ammonia power plant to high pressure to drive a turbine (FIG. 1) forgeneration of auxiliary power that augments the output power obtainedfrom the main steam turbine [not included in any drawing here]. Thepartial ashes collected in the chamber (FIG. 5) including those on thesurfaces of ammonia super heater is regularly removed using anyconventional method. The arrangement for ash removal can be either onthe left or right side of ammonia super heating chamber (FIG. 1),depending on the temperature needed for auxiliary power generation. Foran ammonia plant with about 10% efficiency, the first arrangement isquite good. For a plant with around 20% efficiency, the secondarrangement is preferred with a special arrangement of ash removal fromthe surface of the ammonia super heater. In this arrangement, the fluegas is not allowed to escape to air and this arrangement increases thepressure of the gas to enable efficient capture of flue gas heat by theammonia super heater that in truns help the ammonia turbine functionwell. After capture of all components, the unreacted nitrogen gas (whichis quite pure) is either released to the air or collected. Thus, thepressure does not build up excessively.

In an alternative arrangement the flue gas from the boiler is directlypassed through the bottom of a chamber [FIG. 5] and passes verticallyupwards through ceramic filters placed horizontally and then throughceramic filters placed vertically in another chamber connected to thefirst chamber. It then heats the ammonia super heater chamber [FIG. 1]before passing through the chamber containing fabric filters. When theentire chamber is well insulated, the ammonia can be heated toconsiderably high pressure and temperature leading to good auxiliarypower generation. The air preheating coil can be conveniently placed inlower section of this chamber (FIG. 5), if needed. In this arrangement,ash deposition on the surface of the ammonia chamber is minimal.Whatever ash is deposited on ammonia super heater surfaces is removedusing any conventional means. However, it is still necessary to havesaid protective coating (as described earlier) on the ammonia chambersurface to prevent corrosion due to toxic flue gases and hightemperature.

Step 3: The flue gas from the said chamber is finally passed throughfabric filter to capture any remaining part (from step 1) of the flyashes. Fabric filter can also capture some of the oxides of mercury[https://hub.globalccsinstitute.com/publications/coal-quality-impacts-and-gas-quality-control-oxy-fuel-technology-carbon-capture-and-storage-cost-impacts-and-coal-value/62-hg-removal-cost-estimation]which are usually solids at the flue gas temperature. These two steps1-2 drop the temperature of flue gas. After passing through the fabricfilter, the flue gas is passed through an electrostatic precipitator(ESP) [FIG. 1] to remove the soot or any smoke particles which are notpreviously captured.

Step 4: In steps (1-2) the anhydrous NH₃ gas after collecting the heatfrom a heat exchanger and from the electrostatic precipitator/fabricfilter (FIG. 1) (both of which retains some part of the flue gas heat)is fed back [FIG. 1] to the ammonia super heater. The said ammonia superheater is embedded in FIG. 5 after the ceramic filters. The anhydrousammonia is superheated at super critical pressure 200 bars attemperature 200° C. by the heat of the flue gas in the chamber(FIG. 5).This leads to the expansion of the ammonia to drive the turbines in anNH₃ power plant so as to generate the auxiliary power. If the flue gasheat is used to pre heat air (APH) used for the combustion of coal, tillthe flue gas temperature drops to 300° F. (150° C.), then the anhydrousNH₃ gas is heated to 100° C. at pressure around 100 bars. In the lattercase, the auxiliary power generated is less than the first case. In thissection, it is necessary that the tubes & vessels containing NH₃ insidethe superheating chamber has an external coating or wrapping ofmaterials that is non-reactive to the toxic gases and with good thermalconductivity. Graphene film could be such a material (1, 2) [1. A Reviewon the use of Graphene as a Protective Coating against CorrosionJianchen Hu, Yanfeng Ji, Yuanyuan Shi , Fei Hui , Huiling Duan and MarioLanzal , Annals of Materials Science & Engineering, —Volume 1 Issue3-2014 ISSN: 2471-0245 www.austinpublishinggroup.com, p.1-16; 2.Impermeable barrier films and protective coatings based on reducedgraphene oxide, Y. Su, V. G. Kravets, S. L. Wong, J. Waters, A. K. Geim,& R. R. Nair, Nature Communications 5, Article number: 4843 (2014),doi:10.1038/ncomms5843]. Other protective coating that is found suitableis discussed in the beginning of this section.

The superheated ammonia [FIG. 1, FIG. 5] drives the turbine (NH₃ turbinein FIG. 1) and produces auxiliary power [see section 1.2]; it undergoesexpansion and cooling. The ammonia is then compressed and passed througha condenser [FIG. 1] which is cooled further by fixed amount of coldwater. The water is cooled by a fraction of cold nitrogen gas (see FIG.1). At point m in FIG. 1, after the collection of liquefied SO₂, thecold N₂ gas stream is divided in two parts; one part goes directly tothe ammonia condenser (FIG. 1) to cool the water, which cools thecompressed ammonia and the other part enters the chamber of NO₂condensation (FIG. 1).

Step 5: After the auxiliary power generation, the compressed ammonia gasis passed from the condenser by a pump through a heat exchanger [FIG. 1]and then passed through the electrostatic precipitator/fabric filter[FIG. 1] and back to the ammonia super heater in the closed cycle. Theammonia gas collects heat from the heat exchanger, fabric filter and ashremoving chamber before passing through the ammonia super heater in fluegas chamber[FIG. 5] to repeat the steps 1 to 4 [FIG. 1]. The latterarrangement is not shown in FIG. 5. The external surface of the tube(s)in fabric filter and ash removing chamber through which the ammonia gaspasses has protective coating. The coating could be similar to thatmention in step 1 above.

Successive Condensation of Mercury Vapor (SO₃ (Boiling Point. 44.9° C.),and Steam and Capture Through Steps 6 to 8

Step 6: The first heat exchanger condenses partially (point 3-4 inFIG. 1) the mercury, the steam, and part of sulfur trioxide gas, SO₃,(boiling point 44.9° C.) which are collected. For this the flue gas ispassed through a coil of tubes as shown in FIG. 6. The coil is enclosedin this heat exchanger. The heat exchanger is described in FIG. 11. Thesaid coil of tubes has special curved sections (FIG. 6) where condensedliquid from the flue gas accumulates while leaving space on the top forthe uncondensed flue gas components to pass without carrying thecondensed fluid. It drains the partially condensed components whichmajorly comprise of steam, mercury. This step partially condenses acidvapors like H₂SO₄, HNO₃ that may be present in the flue gas from powerplants [Edwards. Rubin, Toxic Releases from Power Plants, Environ. Sci.Technol. 1999, 33, 3062-3067]. These acid vapors along with some partHCl (hydrochloric acid) and other acid vapors are dissolved also in thepartially condensed steam (water). The latter contains small amount ofliquid SO₃ which is dissolved in the condensed water of the steam. Thedraining of these condensates occurs with the automatic opening of thevalve when enough liquid pressure is built up (FIG. 6). At this stagesmall amount of mercury is also drained. Alternatively, the opening ofthe valve can be arranged electronically (not shown in in FIG. 6 or 1)when condensates reaches a certain level.

Step 7: After fly ash, steam, mercury and SO₃ is collected by steps 1 to6, the flue gas contains mostly N2, CO₂, and a small percentage of SO₂,oxides of nitrogen and carbon monoxide in very small amount. After steps1 through 6, the flue gas is cooled further by passing through coils(FIG. 6) in a heat exchanger (between a and b₁ in FIG. 1). The heatexchanger (shown in the section a-b₁ in FIG. 1) contains water at thispoint and is cooled by passing cold N₂ gas coming from the right throughturns of tubes (FIG. 11) immersed in the water. This N₂ gas is in thelast leg of its reverse journey before being vented out to atmosphere orbeing collected as pure nitrogen, if needed. This is the unreactednitrogen of the flue gas (the production of which is explained in Steps14 and 15). The flue gas, which is cooled to less than 50° C. throughthis heat exchanger, is then compressed adiabatically to about 2 to 3bars [b₁ to b₂ in FIG. 1]. This compressed gas is cooled further bypassing the compressed gas at b₂ through tubes immersed in water in achamber [either FIG. 7 or FIG. 6 combined with FIG. 11] that ismaintained around 35° C.±2 through controlled flow of cold nitrogen atlow flow rate and using radiator cooling, if necessary, by solar poweredfans. The radiator is not shown in FIG. 1. The cold nitrogen gas entersthe chamber from right in FIG. 1 in section b₂-b₃. Appropriatetemperature controller is used at this stage that controls the flow ofthe said cold nitrogen gas and the water in the chamber (FIG. 7 or FIG.11 containing FIG. 6) is stirred to have uniform temperature. It may benecessary to have more than one such chamber if the flow rate of theflue gas is high to ensure condensation of SO₃ and significant part ofsteam H₂O [section b₂-b₃]. This will increase also the part of acidicgases that dissolves in the condensed water. Here, significant mercuryvapor in the flue gas also condenses to metallic elemental liquidmercury and is collected in a container (not shown) that is connectedbelow the water tank. The mercury may be mixed with water (fromcondensation of steam) and also with HCl or SO₃ which are dissolved inthe condensed steam (water). As mercury is much heavier (density 13.6g/cc) than water (1 g/cc), mercury will be collected at the bottom ofthe tank and it is drained out separately through taps. This stage ofFIG. 7, or FIG. 6 with FIG. 11 is inserted in section b₂-b₃ of FIG. 1along with a compression pump [not shown in FIG. 1].

The arrangement of the configuration of the flow tubes through whichflue gas passes is shown in FIG. 7 and FIG. 6 combined with FIG. 11. Inthis section, to capture SO₃, H₂O, and mercury(Hg) vapor, the chambercontains fixed amount of water that is cooled by the said cold nitrogengas passing through turns of tubes one end of which is connected at theport X₁, which would be coiled around the flue gas tubes (not shown) inFIG. 7 with the end being connected to the exit pipe Y₁Y₂ [FIG. 7]. Theexternal surfaces of the both the tubes of (FIG. 6-8) would be madeblack with paints that have good thermal tolerance (at low temperaturesas well as at temperatures of ˜80° C.). This would ensure good thermalradiation from the flue gas tube which in turn would ensure good heatexchange through helium gas and the conducting pebbles (for capture ofcomponents with b.pt below 0° C.). The port Y₁Y₂ is connected to otherinlets in other sections where such figure (say, FIG. 7) is referred toand where cold nitrogen gas is used to cool the compressed flue gas (forcapture of components with b.pt below 0° C.). However, near the point ain FIG. 1 which represents this part (step 7) of the process, thenitrogen gas exiting at Y₁Y₂ reaches the ambient temperature. It is purewhen the said N₂ gas is passed through turns of tubes(not shown)surrounding the tubes in FIG. 7 or in FIG. 11, the end of the N₂ gascarrying tubes being connected to the exit port (say, Y₁Y₂ in FIG. 7).The N₂ can be vented out by the emission capture plant or collected atthis point for sale/industrial use, since it has no further use incooling and it must be exited from the emission capture plant. However,chamber of FIG. 7 is used also at other steps. The cold N₂ gas exitingfrom Y₁Y₂ in other steps is connected to the inlet of another separatecooling chamber of FIG. 7. In many steps where the flue gas is to becooled below 0° C., the chamber of FIG. 7 does not contain water asmentioned earlier in the description of drawing of FIG. 7.

Proper stirring of water (in the chamber of FIG. 7 or in FIG. 11) in forstep 7 is needed to have uniform cooling of water (for capture of fluegas components that have b.pt above 0° C.).

The water temperature is kept at 35° C.±2 in this step 7 [through use ofa temperature controller, sensor and flow controller of cold N₂ gas,fans for the heat radiator—these are not shown in FIG. 7] to condenseSO₃ & H₂O which is collected at the bottom as shown in FIG. 7 or FIG. 6.Some of the acid vapors in the flue gas gets dissolved in the condensedwater. This mixture of dissolved acids, SO₃ & H₂O may also containpartly condensed mercury, which, however, is heavier and will settle atthe bottom. If the flue gas is obtained by burning low sulfur contentcoal, then it is expected that the sulfuric acid formed in the collector[FIG. 6 or FIG. 7] will be fairly dilute. If the flue gas is obtained byburning coal with high sulfur content (similar to Indian coal) then thesulfuric acid formed in the container [FIG. 6 or FIG. 7] may be slightlyconcentrated. In most of the cases it would be dilute since SO₃concentration is quite less than that of SO₂ in coal fired power plant.Part of the captured mercury may form compounds with the captured HCland sulfuric acid [H₂SO₄] in the collection chamber. The compoundhowever will be dissolved and in the form of liquid which can be drainedout. The part of the condensed mercury may be collected at the bottom ofthe container in FIG. 6 or FIG. 7.

It may be mentioned that with the current existing state-of-the-arttechnologies, in case of a coal fired plant, powdered activated carbon(PAC) is injected into the flue gas for mercury capture [1](Moretti andJones. 2012). This process costs $45000.00 per pound of Hg removed and$5 million to 6.75 million annually for a 500 MW power plant[1a,b,c,d].In general, the cost of mercury removal with existing technologies ishigh [61,61a]. With this new technology, no such injection of materialsis needed. This new technology described in this invention is veryeconomical, since only electrical power is used to compress the flue gasand to obtain cold N₂ gas at the end. SO₃ of the flue gas [from coalfired power plants] also liquefies and is collected. Mercury, beingheavier, will collect at the bottom. Alternately, both mercury vapor andSO₃ can be collected separately in two chambers maintained at 53° C.(for Hg) and 35° C. (for SO₃) respectively. This process would not beneeded if the flue gas comes from natural gas fired power plants. Thecontrol of the temperatures is done through a temperature controlcircuit (not shown in FIG. 1) that regulates the flow of cool nitrogengas through the water. The internal parts of the compressors have someprotective coating so that the compressors are not corroded by toxiccomponents of the flue gas. Such corrosive characteristics is reducedsignificantly as the flue gas temperature drops successively in thisinvention.

Step 8: After step 7, the flue gas containing remaining SO₃ underpressure is further cooled by passing through heat exchanger and thencompressed to ˜4.5 Bars and passed through tubes immersed in a watertank (c₁ in FIG. 1) similar but different to that of FIG. 6 or FIG. 7but maintained at around 25° C. by passing controlled amount of saidcold nitrogen gas and using temperature controller (not shown in FIG.1). In this section (stage c₁ in FIG. 1), SO₃, as well as any leftoversteam is further liquefied and collected in a chamber connected belowthe water tank. Mercury (boiling pt. 356.73° C.) is majorly condensed insteps 6 & 7. Some of the remaining mercury is also condensed in thisstep 8. Any mercury vapor that condenses along with SO₃ or water fromsteam will settle at the bottom (FIG. 6) and can be separated bygravity. This happens in process at c₁ in FIG. 1. In this chamber, moresteam from the flue gas will be collected. Thus, the sulfuric acidformed from the dissolved SO₃ in condensed steam is dilute. The internallinings of the tube in FIGS. 6, 7 & 8 should have protective coating assaid earlier.

Capture of Nitrogen Dioxide NO₂ (b.pt 21° C.)

Step 9: To separate NO₂ (boiling point 21° C.), the compressed flue gasis further cooled by passing through tubes (not shown) inside a heatexchanger (after c₁ in FIG. 1). It is then compressed adiabatically (to˜6-7 bar). This compression is done in two stages. The first compressedgas (3 to 4 bars) is cooled (˜18-19° C.) by passing through tubes insidea heat exchanger, which is cooled by said cold N₂ gas (not shown in FIG.1). The flue gas is further compressed (6 to 7 bars) and cooled bypassing through tubes (FIG. 7) kept immersed in water in a differentchamber (FIG. 7), cooled by controlled flow of cold N₂ (from the right)through the chamber (c₂ in FIG. 1), which is maintained at 8° C.±2. Thisis the third chamber of FIG. 7. This process will condense and separateliquefied NO₂ from the flue gas. In this step the most of the acidvapors HNO₃ (b.pt 83° C.) and H₂SO₄ (b.pt 337) , if present in flue gas,are also condensed. These will also dissolve in the water condensed fromthe water vapor in the flue gas. This step will also condense andseparate most of the remaining mercury vapor in the flue gas. It willfurther separate the water (in the form of steam) in the flue gas. Thisstep is also performed at stage c₂ of FIG. 1. It is necessary toseparate/condense all the steam of the flue gas ahead of subjecting thesaid flue gas to cryogenic processes below 0° C. in the steps describedbelow, so that compressors are not chocked (due to ice that can formbelow 0° C. if the flue gas has steam) when compressing flue gas below0° C. Liquefied NO₂ and water (condensed steam) may be mixed in thecollection chambers of either FIG. 6 with FIG. 11, FIG. 7 or FIG. 8.FIG. 8 could be an alternative collection chamber to FIG. 7 for thisstep. In the case of flue gas from natural gas fired power plants, thisstep will condense most of the water vapor of the flue gas. This isimportant so as to prevent the formation of solid ice in the lattercryogenic stages. Formation of ice during the cryogenic processes atlatter stages can choke the compressors and expansion valves etc.

Capture of SO₂

Step 10: After step 9 the flue gas contains mostly SO₂, CO₂, N₂O, NO,CO, unreacted nitrogen/oxygen, some traces of noble gases etc. In thisinvention henceforth we call the unreacted nitrogen/oxygen, some tracenoble gases etc. as simply “nitrogen, N₂”, as N₂ is the major component.The flue gas after step 9 is further compressed gas is furthercompressed to pressure around 8-9 bars (in section c₃-d in FIG. 1). Thecompressed gas is passed through coils kept in a chamber as shown inFIG. 7, but without water and kept at ˜−14° C.±2. For collection ofliquefied SO₂, CO₂, N₂O, NO, CO, each separately, the chamber (FIG. 7,FIG. 8) does not contain any water as mentioned earlier and thearrangement is mentioned in the part B description of drawing of FIG. 7.

For step 10, the said chamber of FIG. 7 (or FIG. 8) is placed betweenthe points d & c₁ in FIG. 1 after the collection of NO₂. The chamber ofFIG. 7 in this step does not contain water unlike those in earlier steps(step 9 and above). It contains heat conducting pebbles or metal chipsthat will facilitate heat conduction from the flue gas tubes to the coldnitrogen gas carrying tubes with the help of helium gas (which has highthermal conductivity) at pressure 1 to 2 bars. Also, the chamber isair-tight with helium gas inside. The helium gas enables good heatconduction for the heat exchange. A small fan inside the chamberoperated by a solar power will circulate the helium gas throughout andthus will further enhance the heat exchange rate in chamber of FIG. 7when used for steps 10-15. Said cold nitrogen gas obtained at the end ofthe whole cycle of operation, is passed at 2 bar through a tube in thischamber [FIG. 7] such that the chamber is cooled at temperature ˜−14° C.by the controlled flow of cold N₂ gas (obtained at the end of thecycle). This cold N₂ flows from the point k of the CO₂ condensation unitin step 11, to the left of FIG. 1. SO₂ is condensed in the chamber ofFIG. 7 kept in the section d-e₁ (FIG. 1) in the form of liquid which iscollected in a tank connected to the coils [FIG. 7 or FIG. 8]. Sucharrangement also allows rapid collection of the liquefied form of SO₂captured from the flue gas. This particular step is not necessary forflue gas from clean natural gas fired power plants as it does notcontain sulfur dioxide. The cold N₂ coming out of the SO₂ condensationchamber at point 1 (FIG. 1] is divided in two parts at point m [FIG.1]—one part directly goes to the ammonia condenser unit to cool thewater (FIG. 1) that is used to cool the compressed NH₃ gas after theturbine expansion in step 4 above. The other part of the cold N₂ entersthe NO₂ condensation chamber. The compression to 8 to 9 bars after step9 can be done in two stages also and the compressed flue gas from thefirst stage can be cooled in heat exchanger before being compressedfurther and entering the chamber of FIG. 7 as discussed in this step.

After this process the flue gas contains mostly unreacted N₂, CO₂, andsome small amount of N₂O, NO and much smaller amount of CO (carbonmonoxide).

Production of Liquefied CO₂ Captured from the Flue Gas: Process (e₁, e₂,e₃) [FIG. 1]

Step 11: is the multi-stage adiabatic (isentropic) compression (FIG. 1)of the flue gas left over from step 1 to 10 above. This step 11 and thefollowing steps (12 to 16) are performed in stages e₁, e₂, e₃, f, g, h &i in FIG. 1. The flue gas mixture after step 10 (i.e., collection ofliquefied SO₂) and coming out at e₁ (in FIG. 1) is compressedadiabatically from initial pressure of about 8 to 9 bars [attemperatures around −10° C.] from steps 9 & 10 above, to a pressure of26.47 bars using the n-stage compressor. The single compressor shown inFIG. 1 after steps 9 & 10 represents a number of compressors. The totalnumber of compressors used in this technology invention is 15. However,it can be adjusted based on the principle discussed later in section1.3.2. This adiabatic (isentropic) compression will raise thetemperature above −10° C. to around −1 to -3° C. The flue gas after eachisentropic compression is passed through heat exchanger (which is cooledby passing said cold N₂ gas) to prevent the temperature rise from −10°C. upward significantly. The finally compressed gas(26.47 bars) ispassed through coils in FIG. 7 kept in section e₂ (FIG. 1), entering atport A of FIG. 7l with the chamber kept at −18° C.±2 [maintained bypassing cold N₂ gas and a temperature controller]; the chamber issimilar to FIG. 7 as said in step 10. In this section, the CO₂ of thecompressed flue gas [at 26.47 bars, the saturation pressure of CO₂ at−10° C.] is converted to a super-cooled liquid CO₂ at −10° C.,corresponding to stage n in FIG. 1. The liquefied CO₂ thus produced iscollected in an insulated container [not shown in FIG. 1 or FIG. 7], tobe connected to chamber at n (LCO₂ collector in FIG. 1) and theremaining flue gas is under pressure 26.47 bars. This is the state e inFIG. 2. Since the N₂ content of the flue gas is around 75% or more [byweight] of the whole flue gas [Rogers and Mayhew (1992)[80], also seesection 1.3.2] , and the entire N₂ gas is cooled to a few degrees aboveits boiling point (−196° C.) in this technology, the cold N₂ gas shouldadequately take care of all the cooling required in earlier steps andthis step. Combined cooling of the water tanks by radiators and fans(run by solar power) in the earlier steps would increase the energyefficiency of the capture process. The insulated chamber collecting theliquefied CO₂ in this step is connected via throttle valve (FIG. 1) tothe flash chamber (FIG. 9).

Production of Dry Ice from the Captured Liquefied CO₂

Step 12: To produce dry ice, the captured liquefied CO₂ at step 11 above(represented by state e in FIG. 2) is throttled adiabatically (frompoint n in FIG. 1) into an insulated flash chamber (FIG. 1 & FIG. 9),placed between points o & p in FIG. 1.l This is shown by state fin FIG.2. Process (e-f) (FIG. 2) is the adiabatic throttling of the liquidcarbon dioxide (CO₂) by an expansion valve to atmospheric pressure atstate fin an insulated flash chamber (FIG. 1 & FIG. 9), where state f(FIG. 2) is a mixture of solid dry ice and vapor, referred to as dryvapor. This process is an irreversible adiabatic expansion; hence thedashed line (FIG. 2). The design of the flash chamber to collect the dryice & vapor is shown in FIG. 9. It has a throttling valve for liquidLCO₂ to enter. It has an inlet for very cold N₂ gas (coming after thecondensation of CO (carbon monoxide) following the 3′ stage of thetriple stage turbine work in FIG. 1) to enter and it has an outlet forthis N₂ gas that enters from the point q to the heat exchanger [FIG. 1].The cool N₂ gas in the chamber of FIG. 9 freezes the dry vapor into dryice and further freezes the dry ice [FIG. 9]. The flash chamber (FIG. 9)contains an outlet with valve v1 for the dry ice at the bottom to entera long column at the end of which there is another valve v2 which opensautomatically by the weight of the dry ice. This arrangement preventsescape of very cold N₂ gas entering the chamber [FIG. 9], while dry iceis continuously formed and collected. The cold nitrogen gas beingregulated to keep the temperature of the flash chamber about −10° C.below −78° C., the sublimation point of dry ice. The super-cooled N₂ gasis obtained by the following steps (steps 14-15). The insulated flashchamber is air tight so that air does not enter from outside. Theremaining flue gas after separation of CO₂ (in liquefied and dry iceform) contains mostly unreacted nitrogen (N₂), nitrous oxide, nitricoxide and some traces of carbon monoxide (ignoring traces of noblegases). This remaining part of flue gas moving in the right after pointfin FIG. 1 still is at a pressure of 26.49 bars.

Separation of N₂O from the Flue Gas

Step 13: After step 12 and production of liquefied CO₂ and dry ice fromthe carbon capture of flue gas, the flue gas coming out of e₂ in FIG. 1is still around −10 ° C. and pressure 26.49 bars. It is subject tofurther cooling by passing through coils (not shown in FIG. 1 ) in heatexchanger at e₃ (FIG. 1 ) to a temperature of −50° C. to −60° C. by thecold N₂ gas entering the said heat exchanger from the chamber of N₂O atthe right in FIG. 1, maintaining the pressure by necessary compression,if needed. The cold N₂ gas from the flash chamber in step 12 enters theN₂O chamber from the right side, through the line marked by the point qin FIG. 1. The cold compressed flue gas then enters the first turbine atpoint f (FIG. 1). It undergoes the first isentropic expansion there(step 14).

Step 14: It is (i) the first isentropic expansion of the compressed fluegas from step 13 (containing mostly nitrogen gas) (from step 14) (atpressure 26.49 bars) in the first stage of a triple-stage turbine to theboiling point of N₂O (−88.5° C.) at a pressure of about 13.27 bars to15.6 bars depending on the initial cooling temperature (−50° C. to −60°C.). To collect the liquefied N₂O, this turbine expanded flue gas fromfirst stage turbine is led to a chamber [FIG. 10] kept ˜−96° C.±2through controlled flow cold nitrogen gas from the right. This causesall the N₂O in the compressed flue gas (at temperature ˜−88.5° C. orslightly higher after the expansion) to condense and liquefy. The liquidN₂O is then collected in an insulating container [FIG. 10]. (ii) In thenext stage, the flue gas at pressure around 15 bars coming out of theN₂O condensing chamber of (i) of step 14, is further cooled totemperature around −106 to −110 ° C. by passing through a heat exchanger(at g, FIG. 1 ) which is cooled by cold Nitrogen gas coming from thepoint q at the right. The heat exchanger can be that shown either inFIG. 7 or FIG. 8. The flue gas is then expanded through the secondturbine (FIG. 1 ) to a temperature of −152 ° C. at 4.87 bars. Theexpanded gas is passed through a chamber kept at −158±2° C., usingcontrolled flow of super cold N₂ that comes right after the third stageof turbine expansion at point I in FIG. 1. A part of this nitrogen (attemperature ˜−194 to −195 ° C.) is fed to this NO capture chamber. HereNO from the expanded flue gas (at pressure 4.87 bars) is condensed tosuper-cooled liquid (NO) under pressure and collected in a similarinsulating chamber (FIG. 10). The liquid NO collection chamber [FIG. 10]is jacketed inside another second chamber that is externally highly wellinsulated container and the inside of this second chamber (similar toFIG. 10] is cooled by controlled flow of said super cooled N₂ gas (FIG.1 ) (which has temperature ˜2 degrees above the boiling point of N₂,obtained at the end of the cycle), so that the chamber is maintained attemperatures ˜−156 to −160° C. The conventional insulators such asalternate combination styrofoam and reflecting aluminum foils or anyform of good insulation works well for the external jacket. Thisarrangement is not shown in FIG. 1. The super cooled nitrogen comingfrom the third stage expansion is split in to two—one goes to the NOcondensation chamber and the other to the CO₂ flash chamber (FIG. 1 ).The stage (i) of step 14 may be avoided if the NO concentrationoverwhelms the N₂O concentration in the flue gas. NB: A triple stageturbine is used rather than a single-stage turbine to avoid thesolidification of NO (freezing pt. of −164° C.) from choking andfreezing the turbine blades before exiting the turbine. In many boileror burner, the N₂O concentration is quite significant relative to NOconcentration and hence stage (i) is necessary. In this invention wefind that it is very important to ensure that the turbine blades do notchoke due to freezing of any of the component of the flue gas.

Production of Super-Cooled N₂ and Capture of CO

Step 15: In this step, the flue gas (mostly nitrogen gas at pressure4.87 bars and temperature around −152° C. to −155° C.) from step 14further undergoes isentropic expansion by the third turbine (FIG. 1) toatmospheric pressure into an highly insulated and air tight andinsulated chamber (not shown). This expansion lowers the temperature ofthe flue gas (mostly nitrogen) close to its boiling point (−195.8° C.)before exiting at state i (FIG. 1 ) to supply very cold N₂ gas for thevarious cooling processes in the system (as described above). Here CO(carbon monoxide) with boiling point (−191.5° C.) is condensed at thebottom of the chamber to a super-cooled liquid [FIG. 10] and it is thendrained out of the chamber into a well-insulated container [not shown inFIG. 10]. The super-cooled nitrogen gas is then pumped (pump not shownin FIG. 1 or FIG. 10) out of the said chamber in reverse direction toperform the various cooling processes as described in steps 6 to 14above. The symbol N₂ is used to denote not only the nitrogen but allalso the inert noble gases present in air which remain unchangedthroughout the combustion reaction, and the negligible unreacted oxygenremaining after the combustion process. The super cooled nitrogen(source of fairly pure nitrogen) obtained at this stage is sent back inreverse direction to perform the cooling in reverse order. Afterperforming all the cooling in reverse order, the nitrogen gas (which isquite pure) reaches ambient temperature at point a, and can be exited inor collected, if needed, as mentioned earlier. It is quite pure (exceptfor the inert noble gas content).

In the steps/processes described above super-cooled nitrogen line issplit twice-once at the point r and then at the point m (FIG. 1). Thesplit lines and all lines carrying cold nitrogen gas in reverse flowdirection, are wrapped with very good thermal insulation material.Alternate layers of glass wool and reflecting aluminum foil wrappedaround such lines with final layers of shining aluminum foil have beenfound to act as very good insulation in this invention. This givesbetter control over the various cooling processes described in thisinvention. If the flue gas from coal fired power plant contains H₂S(b.pt. −60° C.) (T5) then it is captured by following the step 13 butpassing the flue gas through a heat exchanger (not shown) placed beforethe heat exchanger at e₃ (FIG. 1 ) and maintaining it at −68° C., usingcold nitrogen gas coming from heat exchanger e₃ on the right, similar tothe processes described above.

1.2 Capture of Flue Gas Heat for Production of Auxiliary Power UsingAmmonia Turbine for High Energy Efficiency of the Capture Process.

In order to add further energy efficiency to this technology forindustrial emission capture, we have incorporated in our technology amethod of auxiliary power production using ammonia turbine. It involvesthe following steps (All steps processes can be found in FIGS. 1, 2 and3):

Process (6-7) is the adiabatic compression of the saturated liquid atstate 6 (FIG. 2) to a compressed liquid at state 7 by the feed pump(FIG. 1: shows the pump).

Process (7-8) is the heating of the compressed liquid NH₃ as it coolsthe flue gas from processes 1 to 4 (FIG. 1) discussed above, where it isassumed to attain a super critical temperature of 200° C. at a supercritical pressure of 200 bars at state 8. This assumption is veryreasonable and attainable with the knowledge that typical temperaturesof exhaust flue gases from gas turbines ranges between 370° C.-590° C.[https://www.engineeringtoolboxcom/fuels-exhaust-temperatures-d_168.html]. Therefore,by controlling flow rate of NH₃ for a particular plant (depending fluegas flow rate) this temperature for NH₃ can be attained. The flow ratedepends on flue gas temperature, concentrations and rate of emissionfrom the power plants.

Process (8-5) is the expansion of the super critical vapor at state 8 tostate 5 [FIG. 3] in a turbine [FIG. 1] to produce the engine motivepower.

1.2.1. An Example—the Application of the Above Methods

The number subscripts in the following example—refer to FIG. 3. Thesubscripts f & g refer to saturated liquid & gas respectively.

Thermodynamics Analysis of the Auxiliary Power Generation from the FlueGas Heat Using Ammonia Turbine

We assess the energy required to liquefy entire CO₂ and to cool theentire unreacted nitrogen gas of the flue gas that would have beenemitted, if the entire generated electrical energy of 1.4×10¹⁸ J in UK(2010) was by using (i) coal; (ii) natural gas, using steps g to m insummary of invention and in steps 11 to 15 of section I.1.

From Thermodynamic Property Table for Ammonia (NH₃), PC Model, we findthat at

State 8 (Super Critical Vapor FIG. 3):—T₈=200° C., P₈=200 bars,h₈=1497.7 kJ/kg (specific enthalpy), s₈=4.0721 kJ/kg (specific entropy)

In FIG. 2): State 5(FIG. 3) is (Wet Vapor):—T₅=25° C., P₅=10.032 bars,s₅=s₈=4.0721 kJ/kg (Isentropic Expansion), v_(f)=0.001650 m³/kg(specific volume of saturated liquid at state 5), h_(f)=298.25 kJ/kg,h_(g)=1463.5 kJ/kg, s_(f)=1.1210 kJ/kg, s_(g)=5.0293 kJ/kg

Therefore, quality (x) of wet vapor is given as

(x)=(s ₅ −s _(f))/(s _(g) −s_(f))=(4.0721−1.1210)/(5.0293−1.1210)=0.7551

Hence specific enthalpy of the wet vaporh₅=h_(f)+x(h_(g)−h_(f))=298.25+(0.7551)(1463.5−298.25)=1178.13 kJ/kg

The turbine work (step 4 in section I.1) is

W _(t2)=(_(s) −h ₅)=(1497.7−1178.13)=319.57 kJ/kg

The feed pump work of compression is

W _(p) =v ₆(P ₇ −P ₆)=0.001650(200−10.032)×100=31.34 kJ/kg

Since v₆=v_(f)=0.001650 m³/kg

Now h₆=h_(f)=298.25 kJ/kg, and hence h₇=W_(p)+h₆=329.59 kJ/kg

The heat supplied is then

Q_(in)=h₈−h₇=(1497.7−329.59)=1168.11 kJ/kg, and the heat rejected in thecondenser is Q_(out)==h₅−h₆=(1178.13−298.25)=879.88 kJ/kg

The net work W_(net)=W_(t2)−W_(p)=(319.57−31.34)=288.23 kJ/kg, and thenet heat is Q_(net)=Q_(in)−Q_(out)=(1168.11−879.88)=288.23, hence network is equal to net heat as expected. Therefore, the thermal efficiency(η) of the ammonia power cycle will be

η=W _(net) /Q _(in)=288.23/1168.1=24.6%

In instances when the temperature of the ammonia gas at state 8 is lessthan the critical temperature, the NH₃ power cycle in FIG. 2 will takethe dashed path described by the Rankine cycle (5′-6-7′-8′-5′) with alower thermal efficiency than the super critical cycle; since the finaltemperature of NH₃ at state 8 determines the efficiency.

1.3. Application of the Above Technology of Auxiliary Power Generationto Assess the Overall Energy Requirement for Capture of EmissionComponents from Power Plants.

As mentioned earlier this new technology requires no use ofchemicals/reagents but energy (to drive the compressors and expanders,coolers etc.) to capture the industrial emissions. We take a specificcase where correct data are available [Dr Clifford Jones, ©2013] andassess the total energy required from the output power on top of theauxiliary power generated by methods as mentioned.

1.3.1. Estimation of Auxiliary Power Generated by the Ammonia Turbine[FIG. 1] in a Specific Case

From Global Trends and Patterns in Carbon Mitigation by Dr CliffordJones [©2013 Dr. Clifford Jones & bookboon.com, ISBN 978-87-403-0465-7]the total electric energy generated in the United Kingdom in2010=1.4×10¹⁸ J. Imagine that this has been generated by steam turbineson a Rankine Cycle with 35% efficiency [this assumption is quite normalin the case of a coal power plant, since the overall coal plant powerconversion efficiency ranges from 32% to 42% [Bright HubEngineering—http://www.brighthubengineering.com/power-plants/72369-compare-the-efficiency-of-different-power-plants/].].Then the total heat supplied to the steam power plants (QT) will be

Q _(T)=(1.4/0.35)×10¹⁸ J=4.0×10¹⁸ J

In general, the combustion efficiencies of power plants are within therange of 70-90% (Rogers and Mayhew 1992) (80). So, in this analysis wehave assumed a typical combustion efficiency of 75%. With thisefficiency, the enthalpy of combustion (H_(e)) for the fuels in thisstudy will be

H_(c)=Q_(T)/η_(c)=(4.0/0.75)×10¹⁸J=5.33×10¹⁸ J. if the total mass (m) ofthe fuel of combustion is known, then the specific enthalpy ofcombustion (h_(c)) will be h_(c)=H_(c)/m, and this is usually referredto as the calorific value of the fuel.

If 75% of the heat of combustion is supplied to the steam boilers, then25% of this heat will be retained by the flue gases, which can then beused for the heat requirement source of our Ammonia power plant, andthis is equivalent to (0.25)(5.33)×10¹⁸J=1.333×10¹⁸ J.

In FIG. 1; since the NH₃ cycle will be cooling the flue gas totemperatures slightly above ambient, the efficiency of combustion(η_(c)) of the NH₃ power plant can be as high as 85%. With proper heatinsulations in step 1 to 5, this can be achieved. With this efficiencyof combustion, the total heat supplied to the NH₃ power plant (Q_(T)) toheat the working fluid will be

Q _(T)=(0.85)(1.333)×10¹⁸ J=1.133×10¹⁸ J

With a thermal efficiency of 24.67% of the NH₃ power cycle, the net workoutput of this power plant will be:

W_(net)=(0.2467)(1.133)×10¹⁸ J=2.795×10¹⁷ J, which will be(0.2795×10¹⁸/(1.4×10¹⁸=19.96% of the total energy generated by the steamturbines.

Therefore, the overall energy generated in a flue gas energy capture bythe combined power cycles of the steam and ammonia power plants in ayear will be 1.4×10¹⁸J+0.2795×10¹⁸ J=1.68×10¹⁸ J. This is a very noveleconomic concept, since billions of dollars of excess energy can beproduced capturing the waste energy globally, by all our power plants ina day.

(i) 1.3.2. Work of Production of Liquid CO₂ from Carbon Capture

Scientific Analysis of the Energy Requirement in the Processes InvolvedSince CO₂ and N₂ are the major constituents of the flue gas from coaland natural gas power plants, and since in our technology nitrogen gasis finally cooled to ˜2 degrees above its boiling point, and this verycold nitrogen gas is used to condense most of the component gases ofsmall percentages, it is sufficient to assess the energy required tocapture the entire CO₂ in the form of liquid and dry ice and the energyrequired to cool the nitrogen gas to near its boiling point. From themethods discussed above, it is obvious that the work of production ofthe liquid CO₂ from carbon capture will involve the difference in thework input to the N-stage compressor and the work output of the nitrogenturbine.

From thermodynamic analysis the minimum specific work done (W_(c)) on anN-stage isentropic compressor is given as

W _(C) =c _(P) T _(X) N[(P _(y) /P _(x))^((1/N)(γ−1)/γ)−1]  (1)

Where c_(P) is the specific heat at constant pressure

T_(x) is the temperature at inlet to each compressor stage

N is the number of stages

P_(y) and P_(x) are the final and initial pressures respectively

γ is the specific gas ratio.

The specific work output (W_(t)) by a turbine is given as

W _(t) =c _(P)(T ₁ −T ₂)  (2)

Where T₁ and T₂ are the inlet and outlet temperatures respectively

Here

T ₁ /T ₂=(P ₁ /P ₂)^((γ−1)/γ)  (3)

For isentropic expansion process

By the energy conservation law, the work done on the compression of boththe CO₂ and N₂ gases in the N-stage compressor is equivalent to the sumof their individual compressions, and for a reduced compression work aspossible, N is taken as 15 (number of compressors) in this study.

The properties of CO₂ are c_(P)=0.8464 kJ/kgK and γ=1.288; and thestates are N=15 stages, P_(y)=26.47 bars, P_(x)=1.01325 bars and T_(x)is taken as 25° C. (298.15 K) after cooling by ambient water. Then fromEquation 1, the specific compression work on the CO₂ gas will be

$\begin{matrix}{W_{C} = {(0.8464)\mspace{14mu} (298.15)\mspace{14mu} {(15)\left\lbrack {(26.12)^{0.0149} - 1} \right\rbrack}}} \\{= {188.51\mspace{14mu} {kJ}\text{/}{kg}}}\end{matrix}$

(T_(x) is the temperature of CO₂+N₂ mixture at state b₁ (FIG. 1 ), andit is assumed to be about ambient i.e. 25° C.).

Also the properties of N₂ are C_(P)=1.0404 kJ/kgK and γ=1.400; and thestates are N=15 stages, P_(y)=26.47 bars, P_(x)=1.01325 bars and T_(x)is taken as 25° C. (298.15 K) after cooling by ambient water. Then fromEquation 1, the specific compression work on the N₂ gas will be

$\begin{matrix}{W_{C} = {(1.0404)\mspace{14mu} (298.15)\mspace{14mu} {(15)\left\lbrack {(26.12)^{0.019} - 1} \right\rbrack}}} \\{= {297.79\mspace{14mu} {kJ}\text{/}{kg}}}\end{matrix}$

For the temperature (T₂) of the nitrogen gas at stage i (i.e. exhausttemperature) (FIG. 1 ) to be achieved at the boiling point of nitrogen(−195.8° C.) (77.35 k) at atmospheric pressure (1.01325 bars) for thecapture of CO (boiling pt. of −191.5° C.), the temperature T₁ at stage g(FIG. 1 ) from equation 3 will be

$\begin{matrix}{T_{1} = {T_{2}\left( {P_{1}/P_{2}} \right)}^{{({\gamma - 1})}/\gamma}} \\{= {77.35\mspace{14mu} k\mspace{14mu} \left( {26.471/1.01325} \right)^{0.2857}}} \\{= {77.35\mspace{20mu} (2.5406)K}} \\{= {196.52K\mspace{14mu} \left( {{- 76.63}{^\circ}\mspace{14mu} {C.}} \right)}}\end{matrix}$

The pressure at stage h (FIG. 1 ) at the boiling point of NO (−152° C.)(121.15 k) for the capture of NO under pressure will be

$\begin{matrix}{P_{h} = {P_{g}\left( {T_{h}/T_{g}} \right)}^{\gamma/{({\gamma - 1})}}} \\{= {26.49\mspace{14mu} \left( {121.15/196.52} \right)^{3.5}}} \\{= {4.87\mspace{14mu} {bars}}}\end{matrix}$

Hence from Equation 2, the specific work output (W_(t)) by the 2-stageturbine will be

$\begin{matrix}{W_{t} = {{1.0404\mspace{14mu} \left( {196.52 - 121.15} \right)} + {1.0404\mspace{14mu} \left( {121.15 - 77.35} \right)\mspace{14mu} {kJ}\text{/}{kg}}}} \\{= {\left( {78.41 + 45.57} \right)\mspace{14mu} {kJ}\text{/}{kg}}} \\{= {123.98\mspace{14mu} {kJ}\text{/}{kg}}}\end{matrix}$

In coal fired power plants the average constituents for 1.00 kg of dryflue gases containing CO₂ and N₂ is estimated at 0.25 kg for CO₂ and0.75 kg for N₂ (Rogers and Mayhew 1992). While in gaseous fuelled powerplants the average constituents for 1.00 kg of dry flue gases containingCO₂ and N₂ is estimated at 0.15 kg for CO₂ and 0.85 kg for N₂ (Rogersand Mayhew 1992).

Therefore, for 1.00 kg of dry flue gases in a coal fired plant, thecompression work input for CO₂ will be (0.25) kg×(188.51) kJ/kg=47.13kJ, and (0.75) kg×(297.79 kJ/kg)=223.34 kJ for N₂, given a specificcompression work input of 47.13 kJ+223.34 kJ=270.47 kJ/kg for themixture of the gases by the energy conservation law.

By the above method, the gaseous fueled (or gas fired) plant will have aspecific compression work input of 281.40 kJ/kg for the mixture of thegases.

Since the specific work output of the turbine is 123.98 kJ/kg, theturbine work from the nitrogen in the flue gases in a coal fired plantis estimated at (0.75) kg×(123.98) kJ/kg=92.99 kJ, and that from agaseous fueled plant is estimated at (0.85) kg×(123.98) kJ/kg=105.38 kJ.

Therefore, the network input into the production of 0.25 kg of liquidCO₂ at state n from a coal fired power plant is estimated at270.47−92.99=177.48 kJ, which is equivalent to 709.92 kJ per kg ofliquid CO₂ at state n [FIG. 1].

Also the network input into the production of 0.15 kg of liquid CO₂ froma gaseous fuel fired power plant is estimated at 281.40−105.38=176.02kJ, which is equivalent to 1,173.47 kJ per kg of liquid CO₂ at state n.

(ii) 1.3.3. Cryogenic Cooling Process of the Nitrogen Gas Contained inthe Flue Gas

We have earlier described in details the methods involved in cooling thenitrogen gas of the flue gas.

The cooling process of the cold N₂ gas at state i starts with coolingthe nitrogen gas from −10° C. to −76.63° C. in process (f-g) (FIG. 1 )and in steps 12 to 14 of section I.1.

The heat reduction in this process for a coal fired plant is given as

0.75×1.0404×(−10+76.63)=0.75×1.0404×dt

dt=66.63° C. (which is the rise in the temperature of the coolingnitrogen in process (i-j)).

Hence the temperature of N₂ at state j will beT_(j)=−195.8+66.63=−129.17° C.

The heat reduction in cooling of the flue gas from ambient temperature(25° C.) to −10° C. in processes (b₁-b₂ . . . d-e₁-e₂ in FIG. 1corresponding to steps 6 to 11 in section I.1) is given as

0.25×258.62+0.75×1.0404×35+0.25×0.8464×35=0.75×1.0404×dt

dt=127.35° C. (which is the rise in the temperature of the coolingnitrogen in processes (j-k-l-m), summary of invention), where 258.62kJ/kg in the latent heat of evaporation of CO₂ at saturated pressure of26.49 bars.

Hence the temperature of N₂ at state m will beT_(j)=−129.17+127.35=−1.82° C. ; which can be used to enhance thecooling of water water in the NH₃ power plant and the multi-stagecompressor.

Similarly the heat reduction for a gaseous fuel fired plant is given as

0.85×1.0404×(−10+76.63)=0.85×1.0404×dt

dt=66.63° C. (which is the rise in the temperature of the coolingnitrogen in process (i-j) in FIG. 1 ).

Hence the temperature of N₂ at state j will beT_(j)=−195.8+66.63=−129.17° C.

The heat reduction in cooling of the flue gas from ambient temperature(25° C.) to −10° C. in the said processes (i.e. steps 6 to 11 in section1.6) is given as

0.15×258.62+0.85×1.0404×35+0.15×0.8464×35=0.85×1.0404×dt

dt=83.90° C. (which is the rise in the temperature of the coolingnitrogen in processes (g to m in Summary of inventions and in steps 11to 15 of section I.1).

Hence the temperature of N₂ at state m will beT_(m)=−129.17+83.90=−45.27° C. ; which can also be used to enhance thecooling of water in the NH₃ power plant and the multi-stage compressor.

Therefore, analyses have shown that with a nitrogen temperature ofT_(i)=−195.8° C. (77.35 K) at state i for both the gaseous and coalfired plants, the cryogenic cooling procedure of the system willeffectively cool the various gases to the required temperatures neededfor carbon capture.

Thus the above analysis shows that using the methods (processes) ofinvention (as described earlier in details) to capture CO₂ from the fluegas emission in the form of liquid CO₂, the net energy required is (i)1,173.47 kJ per kg of liquid CO₂ from the flue gas from natural gaspower plants; (ii) 709.92 kJ per kg from coal power plants.

I.4. Total Energy Required for Carbon Capture vs Output Power:

a. I.4.1 From Natural Gas Power Plants:

Also, from Global Trends and Patterns in Carbon Mitigation by DrClifford Jones, if gaseous fuel (methane) is used in generating the1.4×10¹⁸ J of electric energy (UK 2010), the estimated CO₂ emitted is198 million tons, which is equivalent to 198×10⁹ kg. In the aboveanalysis of a gaseous powered plant the energy required to produce 1 kgof liquid CO₂ is estimated at 1,173.47×10³ J/kg, therefore, the totalenergy required to produce 198×10⁹ kg of liquid or dry ice CO₂ will beequivalent to 198×10⁹ kg×1173.47×10³ J/kg=2.323×10¹⁷ J.

Now as shown earlier the auxiliary power generated by the ammonia powerplants is: 2.795×10¹⁷ J. Thus the auxiliary power generated by theammonia turbine is sufficient enough to capture the entire CO₂ of theflue gas emission from natural gas power plants. No extra power shouldbe necessary from the output power of the plant for the said emissioncapture from natural gas power plants. As mentioned earlier in theprocess the N₂ gas is cooled a few degrees above its boiling point andit is sufficient to condense all the nitrous oxides and CO of the fluegas (flue gas from natural gas fired power plants does not containusually sulfur oxides, mercury, HCl, H₂S etc.). Thus entire capture ofemissions from the natural gas power plants can be accomplished usingonly the auxiliary power generated by the new technology of thisinvention. The total output power of the plant will remain untouched inthis technology for natural gas power plants. As it does not require anychemicals/reagents unlike all existing technologies, it is the mostsuperior and cheapest of all existing other clean energy technologies.

Average cost of electricity in USA is about $0.12 per kWH. With thisrate the cost of converting the entire CO₂ to LCO₂/frozen dry ice is$5.76×10⁹, if the entire energy 1.4×10¹⁸ J is generated by natural gaspower plant and no auxiliary power is generated using the heat of theflue gas. Now at the current market price, LCO₂ sells at $160 per tonwhile dry ice sells at $2-$6 per kg. Even after adoption of thistechnology when LCO₂ will be abundantly available, if LCO₂ sells as lowas $0.10 per kg and the frozen dry ice is sold at $0.15 per kg, theentire cost of capture ($5.76×10⁹) of 198 million ton of LCO₂ will willbe well-paid off through sale of only a fraction of the total capturedLCO₂/or dry ice. It would be quite profitable for natural gas firedpower plant to implement the new technology discussed in this paper.Even if the auxiliary power generation (as discussed in this invention)is completely avoided, still cost of capture of entire emissions fromnatural gas power plants can be realized by selling only 10% of thecollected liquefied CO₂ or frozen dry ice at only $0.15 per kg. Both theliquefied CO₂ and frozen dry ice are sources of very pure CO₂ gas, whichhas many technological uses. If auxiliary power is generated asdescribed in this invention then the entire capture of CO₂ and theassociated toxic products contained in the flue gas from natural gaspower plants can be accomplished without using any additional energyfrom the net power output and thus at no additional cost (excluding themaintenance of the plant and labor) to the power plant. The latter willgain hugely through sales of the products (specially, LCO₂ and frozendry ice) captured using the methods of this invention.

If auxiliary power is not used or generated as described in thisinvention, then the total cost of CO₂ capture in the form of LCO₂ orfrozen dry ice from the flue gas of natural gas power plants amounts to$7.41×2.232/1.305=$13.17 per ton.

I.4.2. From Coal Power Plants

If coal fuel (80% carbon content) is used, the estimated CO₂ emitted is587 million tons for the energy generation of 1.4×10¹⁸ J of electricenergy (UK 2010), which is equivalent to 587×10⁹ kg. In the analysis ofa coal fired plant using our methods of invention as described above,the energy required to produce 1 kg of liquid CO₂ is estimated at709.92×10³ J/kg; therefore, the total energy required to produce 587×10⁹kg of liquid CO₂ is equivalent to 587×10⁹ kg×709.92×10³ J/kg=4.17×10¹⁷J. Subtracting the auxiliary energy generated by the ammonia plant, thenet energy required from the total output energy=4.17×10¹⁷ J−2.795×10¹⁷J=1.305×10¹⁷ J. This is just about 9% of the original total outputenergy before the auxiliary power plant and carbon capture. With $0.12per kWh, this would cost=$0.12/kWhx1.305×10¹⁷ J/3600000 J/KWh=$4.35 BN.This means the net carbon capture cost of $7.41 per ton of CO₂ capture,the auxiliary power is generated as described in this invention. If theauxiliary power is not generated, then the cost is $23.1 per ton ofLCO₂/dry ice captured. This is much lower than the projected and aimedcost of CO₂ at $30 per ton with current state-of-the art aminetechnology(ies)[Refs T1-T4,Z1-Z5, see also references 62-80]. It is tobe noted that the liquefied CO₂ is a source of very pure CO₂, the puritybeing much higher than that of the gaseous CO₂ captured with the currentstate-of-the-art amine or any other technology used for carbon capturefrom flue gas. The purity of the CO₂ in the captured LCO₂ and the frozendry ice is so high that it can be easily used in food industries,electronics industries, and research laboratories, unlike the CO₂captured with chemical based technologies.

The current cost of CO₂ capture by amines technique stands at $52-77 perton. The minimum cost with the existing amine based technique of carboncapture is $65 per ton of CO₂ gas from the flue gas (Luis M. Romeo,Irene Bolea, Jesús M. Escosa, Integration of power plant and aminescrubbing to reduce CO₂ capture costs, Volume 28, Issues 8-9, June 2008,Pages 1039-1046];[https://hub.globalccsinstitute.com/publications/global-status-ccs-2014/74-carbon-capture-cost].For second-generation technologies (defined as those technologies thatwill be ready for demonstration in the 2020-25 time frame withdeployment beginning in 2025) the US DOE has targeted a goal of reducingcapture cost to around US$40/t CO₂ [Carbon captureCost-https://hub.globalccsinstitute.com/publications/global-status-ccs-2014/74-carbon-capture-cost].Moreover, the current technologies including the amine based ones cannotregenerate CO₂, which will be as pure as that available with our methodsof invention described above.

With our technology of invention the cost of capture of CO₂ from coalpower plants would be $4.2 per ton, if auxiliary power is used and$13.42 per ton, if auxiliary power is not generated (assumingelectricity rate $0.12 per kWh). Thus our technology is far more costeffective than any existing technologies and the technologies envisionedby DOE up to 2025 with or without the use of the auxiliary powerdescribed in this invention. Moreover, with amine technologies, SO_(x),NO_(x) and mercury must be scrubbed using other existing technologieslike FGD, SCR etc [1c-80]. The operating costs are very high. If SO_(x)and NO_(x) are captured by amines, amines would be lost and thetechniques would be much more costly and prohibitive. With our newmethods of invention, the vast amount of unreacted N₂ of the flue gas iscooled a few degrees above the boiling point. This cold nitrogenaccomplishes the capture of SO_(x), NO_(x) and Hg without any additionalrequirement of energy and hence cost.

The cost of pure liquefied CO₂ is $128 to $160 per ton and cost of dryice is much more than this. Even at half of this price the 587 MT ofpure LCO₂ would fetch $37.5 BN. Thus, by selling only a fraction of thecaptured LCO₂ or frozen dry ice, the capture cost will be paid off witha very good profit left for the power plants with this technology. Thenew technology allows complete capture (100%) of CO₂ and the toxic gasessuch as SO₃, SO₂, NO₂, NO, CO etc. each separately. It involves no useof chemicals or reagents unlike the existing state-of-the-arttechnologies for clean coal and only fixed amount of water, that can berepeatedly used by methods described in this invention. The additionalcost of capture of these toxic gases with the new technology isinsignificant compared with the huge cost with existing besttechnologies, as discussed in the beginning.

*An overview of current status of carbon dioxide capture and storagetechnologies—Edward S. Rubin, John E. Dawson, Howard J. Herzog,International Journal of Green House and Gas Control, vol. 40, P.378-400. https://doi.org/10.1016/j.ijggc.2015.05.018

II. The Major Advantages of the New Technology Over the ExistingTechnologies in Capturing Industrial Carbon

-   -   a. Our technology is far more economical and cost saving        compared to existing technologies of carbon capture and        including those cryogenic capture technologies that have been        attempted in the past [Ref. T1,T2,T3,T4]. Cryogenic capture        technology in the past required 660 kWh of energy per ton of        CO₂. With our technology, excluding the auxiliary power        generation, it requires 197-198 kWh of energy per ton of        captured liquefied CO₂, if flue gas is from coal power plant.        With the auxiliary power, the technique requires only 62 kWh of        energy per ton of liquid CO₂ or dry ice capture. For the flue        gas from natural gas power plant, our technology requires 327        kWh of energy per ton of LCO₂ capture, if we exclude auxiliary        power generated from the heat of the flue gas. The auxiliary        power generated is sufficient enough to capture the entire CO₂        emissions from natural gas power plants, without putting any        stress on energy output. Thus our technology is superior to that        of the past cryogenic technology. Our technology is much energy        efficient compared to the amines techniques of CO₂ separation        from flue gases. The energy requirement in the amine        technologies range from 3×10⁹ J (833 kWh) to 3.7×10⁹ J (1027        kWh) [Z1-Z4] per ton of CO₂ capture, which is much higher than        that of our technology. With or without the auxiliary power        generation method of our technology, the net energy stress is        the minimal of all existing technologies of CO₂ capture. The        overall cost of capture of CO₂ by amine-based technique stands        currently at $52-77 per ton. Moreover, unlike existing        technologies of CO₂ capture, our technologies capture all        components of flue gas emissions including mercury, sulfur        oxides, nitrogen oxides and carbon monoxide. With the existing        technologies, capture of these components involve huge        additional capital and operating costs as they require constant        use of chemicals/reagents. Even with the current state of the        art amine scrubbing of CO₂ there is continuous loss of amine        which must be replenished, adding to the capture cost.    -   b. Our technology captures industrial carbon dioxide in the form        of liquefied or frozen (dry ice) which is a very pure form of        carbon dioxide unlike the impure carbon dioxide captured with        existing technologies. The liquefied or dry ice form of CO₂ has        tremendous industrial applications and can be used up faster        than gaseous CO₂. These can also be easily stored in        well-insulated container much longer than gaseous CO₂ which        require high pressure vessel. It can be transported to far        distance better than gaseous CO₂. Unlike the current        technologies where captured CO₂ in gas form must be transported        to empty coal or oil field for storage, the CO₂ captured by our        technique can be very easily applied for industrial uses.    -   c. The cost of capture with our technology can be recovered by        selling a small fraction of the captured LCO₂ or dry ice. The        other captured products can also find good market.

We claim

-   -   1. A very cost effective and energy efficient technology of        capturing industrial emissions (mercury (Hg) and its oxides,        sulfur dioxide (SO₂), sulfur trioxide (SO₃), nitrogen dioxide        (NO₂), carbon dioxide (CO₂), nitrous oxide (N₂O), nitric oxide        (NO), carbon monoxide (CO)) contained in the flue gas from coal        and natural gas fired power plants (all older and newer        versions), cement plants and industrial plants in general, each        component separately from each other and in the form of        industrially useful product that can be conveniently stored, and        thus to prevent or reduce/mitigate global warming/climate        change/environmental pollution/health effects arising due to        such gaseous emissions from the said industries into atmosphere        & environment and thus to ensure clean air/environment, using or        requiring no chemical reagent and no external cryogen, but only        a small fraction of electrical power from the output power of        the plants or using the said needed electrical power from any        other source and fixed amount of water that can be repeatedly        used during the capture process, comprising the steps of:    -   a) Generation of auxiliary electrical power using the heat of        the flue gas [in order to reduce the amount of power needed from        the output of the power plants to run the engines of the various        processes of the cryogenic capture technology] using a turbine        that can use anhydrous ammonia contained in an ammonia        super-heater, which is heated by the heat of the flue gas, the        heat absorption of the said super heater being enhanced by        coating on its surface a film of materials with high heat        absorptivity and low emissivity and its placement in an        insulated chamber containing ceramic filters to filter out the        ashes & soot of the flue gas;    -   b) passing the flue gas through ceramic filters, fabric filter,        ESP (Electrostatic precipitator), which capture partially the        heat, the ashes, soot/floating particulates and partially the        mercury and its oxides, with arrangement for removal of the        ashes;    -   c) reheating the ammonia after the turbine work by passing        through the fabric filter & ESP in reverse direction;    -   d) using successive compressions [after the ammonia power        generation (claim 1a)] to specified pressures, successive        cooling through use of specialized heat exchangers and        successive adiabatic expansions of the said flue gas, throttling        of liquefied CO₂ when necessary;    -   e) further cooling of the nitrogen (N₂) gas of the flue gas to a        few (about 1 to 2) degrees above its boiling point (−196° C.)        for using the said cold N₂ gas (by flowing it in reverse        direction) to cool the flue gas at different steps, for        individual capture (separation) of the components;    -   f) cooling in process 1d) being accomplished by (i) passing        adiabatically compressed flue gas through heat exchangers        containing special tubes immersed in fixed amount of water, for        capture of components with boiling points above 0° C., the water        being cooled by flow of said cold nitrogen gas through turns of        tubes that surround the turns of tubes of the flue gas and        radiative cooling arrangement, if the latter is needed;    -   g) by passing adiabatically compressed flue gas, for individual        capture of its components with boiling points below 0° C.,        through heat exchangers containing (i) metal chips/or conducting        pebbles on racks surrounding the turns of tubes carrying said        cold nitrogen gas which in turn surrounds the turns of tubes        carrying the said flue gas, all being embedded in the chambers        of the said heat exchangers and (ii) helium gas that provides        good heat conduction (exchange) between the flue gas tubes and        the tubes carrying cold nitrogen gas and the pebbles/metal        chips, which are cooled by the said cold nitrogen gas which has        temperature just about 2 degree C. above its boiling point        (−196° C.) produced through the third stage turbine expansion,        following the step of capture of nitric oxide of the flue gas        towards the end of a process cycle;    -   h) superior control of cooling the flue gas to desired        temperatures as required for capture of individual components of        the flue gas, each separately through methods of claim 1f) &        1g), compared to heat exchanger chamber where cold nitrogen gas        directly surrounds the said turns of the flue gas tubes as the        nitrogen gas directly enters through the inlet port and leaves        through the outlet port of the chamber;    -   i) repeating the compression, cooling (as in (ii) of 1e) and        expansion successively for 15 to 20 stages, or as necessary,        depending on the initial flue gas temperature and concentration        of the components;    -   j) fractionally liquefying or freezing each component of        emissions at specific temperature and pressure using the        processes of claims 1a) to 1i) for cooling the flue gas and        using controlled amount of the said super cooled nitrogen gas in        successive stages of compression, cooling and expansion;    -   k) using methods to control the temperatures of the chambers to        specified temperatures by control of the very cold nitrogen gas        obtained by method of claim 1e) and through use of specialized        heat exchangers of claim 1f) & 1g), standard temperature        controller and standard flow controller device;    -   l) using methods of special coating to prevent corrosion of flow        tubes, compressors, etc. due to corrosive components of the flue        gas and using flow tubes of special materials to ensure very        good thermal conduction of heat between hot flue gas and the        cold nitrogen gas carrying flow tubes which are all embedded in        the said chambers of heat exchangers;    -   m) utilizing the work generated during turbine expansion (near        the end of a cycle) of compressed N₂ for aiding compression of        flue gases in successive previous stages employing the n-stage        compressors and thus to increase energy efficiency of the whole        capture process;    -   2. A method of capturing and production of liquefied CO₂ and        frozen CO₂ (dry ice), liquefied SO₂, liquefied SO₃, liquefied        NO₂, liquefied N₂O, liquefied NO, liquefied CO and pure nitrogen        gas, each separately, from the flue gas of coal or natural gas        power plants/industrial plants in general, without use of any        chemical/reagent, except fixed amount of water and a small        amount of energy and with a single equipment, at operational        cost far lower than that of any technology of industrial        emission capture hitherto available and at costs far lower than        that of corresponding industrial productions of the said        components, each in fairly pure form that is industrially        usable;    -   3. An equipment for very cost effective and energy efficient        capture of emission components from industrial flue gas, without        using any chemical/reagent and using fixed amount of water that        is repeatedly usable and for production of large amount of        liquefied CO₂ and frozen dry ice, which are sources of very pure        CO₂, comprising        -   a. chambers containing specially designed ceramic filters to            remove fly ashes including oxides of mercury;        -   b. fabric filters and electrostatic separators to remove            soot, smokes, any floating particles etc.;        -   c. ammonia super heater with ammonia turbine for auxiliary            power generation using the heat of the flue gas with the            surface of ammonia super heater chamber been coated with            films of high heat absorptivity and low emissivity;        -   d. pump & heat exchanger for the ammonia after turbine            expansion to capture some of the heat captured by the fabric            filter & electro static separator from the flue gas, before            the ammonia being fed to the ammonia super heater;        -   e. heat exchangers with collecting chambers for cooling and            capturing components of flue gas (Hg, steam, SO₃, NO₂, acid            vapors etc.) with boiling point above 0° C., with said heat            exchangers containing water, which is cooled by passing cold            nitrogen gas, and using flue-gas flow tubes made of special            materials that can stand temperature ˜300° C. and with high            heat conductivity and non-corrosive to the toxic components            of the flue gas;        -   f. heat exchangers for cooling and capturing components            (SO₂, CO₂, N₂O, NO, CO) of flue gas with boiling point below            0° C. to specific temperatures at different stages, the            cooling being accomplished by passing very cold nitrogen gas            (obtained at the end of a cycle of processing the flue gas)            in reverse direction, through the turns of tubes that            surround the turns of tubes carrying flue gas, all being            embedded in the said heat exchanger;        -   g. the said heat exchangers (1f) containing conducting            pebbles or metal chips arranged on racks surrounding the            flue gas flow tubes and containing helium gas for superior            heat conduction (for capture of components with boiling            point below 0° C.) between the flue gas in the flue gas flow            tubes and the much colder surrounding obtained by passing            the said very cold nitrogen gas in reverse direction,            through the turns of tubes that surround the turns of tubes            carrying flue gas;        -   h. flue gas-flow tubes and cold nitrogen gas flow tubes            being made of special materials that can tolerate            temperatures up to 300° C. and low temperatures down to            −194° C. and that have high thermal conductivity, the flue            gas flow tube surfaces being painted black for superior heat            radiation for faster cooling of flue gas;        -   i. special chambers for condensation of Hg, SO₃, NO₂ gases            and collection of the corresponding liquids;        -   j. compressors to compress flue gas at specific temperatures            at different stages to specific pressures and temperatures;        -   k. special chambers for condensation of CO₂ of flue gas and            for rapid collections of liquefied CO₂ as needed;        -   l. flash chambers for throttling of liquefied CO₂ and            arrangement of dry ice by passing very cold nitrogen gas &            rapid collection of dry ice CO₂;        -   m. turbine expanders for expansion of flue gas at specific            pressures and temperatures;        -   n. special chambers for rapid condensation & collection of            liquefied N₂O, NO and CO;        -   o. split lines to inject cold nitrogen gas at different            stages of capture of flue gas components, this being            accomplished by reverse flow of cold nitrogen gas obtained            after third turbine expansion at the end of the process            cycle;        -   p. cold nitrogen feedback lines and means of using very cold            nitrogen gas for cooling the incoming flue gas through            appropriate heat exchangers;        -   q. methods of good thermal insulation for the split and            feedback lines of super cold nitrogen gas;        -   r. standard temperature controller and pressure controller            for nitrogen gas flow;    -   4. Methods of claims 1-2 through the use of equipment of claim 3        further comprising steps to extract the heat of the flue gas and        convert it to auxiliary power, using (i) anhydrous ammonia super        heater with coating of films of high heat absorptivity and low        emissivity material on its external surface, the super heater        being situated in the second chamber employed for capture and        removal of ash/mercury oxides from flue gas, (ii) raising the        pressure of ammonia to around 200 bars and temperature 200° C.        (for efficiency around 20%) when the flue gas temperature is        around 500° C. or to around 100 bars and temperature 100° C.        (for efficiency around 10%) when the flue gas temperature is        dropped to around 150° C. due to use of air pre-heating        (APH); (iii) using turbine for the auxiliary power        generation (iv) heat exchanger processes that also condense        partially, the mercury, the steam and the SO₃ (sulfur trioxide)        of the flue gas in specialized chamber [the condensate being        drained out or collected, as needed] (iv) pump to compress the        said turbine-expanded ammonia and to pass the compressed ammonia        through a condenser to cool (using part of cold nitrogen gas        diverted in reverse direction after capture of SO₂); (v) passing        the condensed ammonia through the said heat exchanger chamber        and the chamber of fabric filter/electrostatic precipitator to        capture part of the flue gas heat trapped there and finally back        to the ammonia super heater to complete the cycle, so that the        auxiliary power is generated in cycles to reduce the energy cost        and to increase the energy efficiency of the capture processes;    -   5. The methods of claims 1 & 2 through the use of equipment of        claim 3 further include steps after reduction of flue gas        temperature through method of claim 4, to condense partially        mercury vapor, steam, SO₃ (sulfur trioxide) including acid        vapors of the flue gas, if any, in specialized chambers embedded        in the said heat exchanger following capture of ashes, mercury        oxides etc;    -   6. The methods of claims 1 & 2 further comprising step to        capture partial steam (H₂O), sulfur trioxide and mercury of the        flue gas by (i) further cooling to temperature less than 50° C.        the flue gas remaining after method of claim 5 by passing the        said flue gas through turns of tubes immersed in water, which is        cooled by passing said cold nitrogen gas through separate turns        of tubes immersed in the said water; (ii) adiabatic compression        to 2 to 3 bars of the said flue gas from method of claim 6(i)        and further cooling of the compressed flue gas by passing        through special chamber containing turns of flue gas flow tubes        immersed in water, with water being cooled and maintained at        35±2° C. by controlled flow of the said cold nitrogen gas        (method of 1e) through separate turns of tubes immersed in the        said water, the said flow being in a reverse direction looking        from the step of the final capture of steam (H₂O), sulfur        trioxide and mercury, as the said components (H₂O, SO₃ and Hg)        condenses to respective liquids which are collected;    -   7. The methods of claims 1 & 2 and the use of equipment of claim        3 further comprise of (i) steps to adiabatically compress the        said flue gas after application of method of claim 6 to pressure        of 4.5 followed by (ii) cooling of the said compressed flue gas        in specialized heat exchanger containing water cooled and        maintained to required temperature (25±2° C.) by passing        controlled flow of said cold nitrogen gas through turns of tubes        immersed in the water of the said heat exchanger, the flow being        in reverse direction (after the NO₂ collection chamber seen from        the right in ways similar to that of methods of claims 6), for        partial capture of steam (H₂O), final capture of sulfur trioxide        and final capture of mercury;    -   8. The methods of claims 1 & 2 and the use of equipment 3        wherein capture of NO₂ in the said flue gas [remaining after        applications of methods of claim 7] in the form of liquid is        accomplished by (i) adiabatic compression of the said flue gas        to 6 to 7 bars pressure and (ii) by cooling to temperature ˜18        to 19° C. [by passing the said flue gas through special chamber,        which is cooled by controlled flow of the said cold nitrogen gas        using methods of claim 6] and (iii) collection of the liquefied        NO₂;    -   9. The methods of claims 1 and 2 through the use of equipment of        claim 3 further comprising steps of (i) adiabatic (isentropic)        compression of flue gas remaining after capture of nitrogen        dioxide (NO₂) [after step of claim 8], to a desired pressure (6        to 7 bars), (ii) cooling of the compressed said flue gas first        to temperature 18±2° C. for condensation of NO₂, acid vapors        like HNO₃, H₂SO₄ and part of steam in the flue gas and (iii)        then cooling the said flue gas to temperature around 8° C.±2 for        complete condensation of any remaining steam, NO₂, the said acid        vapors of the flue gas to prevent chocking of the compressors        compressing the said flue gas below 0° C. in later stages, (iv)        further compression of the flue gas remaining after complete        condensation of steam to desired pressure (8 to 9 bars) (iv)        passing the said adiabatically (isentropic) compressed gas        through special heat exchangers where inside temperature is        cooled to ˜−14° C. to −16° C., for complete capture SO₂ of the        flue gas in the form of liquid SO₂, the required cooling being        accomplished by passing in reverse direction the said cold N₂        gas coming from the point of capture of liquid CO₂ through turns        of tubes that surround the turns of tubes carrying the flue gas        in separate heat exchanger that does not contain water but        conducting pebbles or metal chips on perforated racks that        surround the said tubes and helium gas around 2 bars to improve        heat exchange between the flue gas and the cold nitrogen gas        [noting that the flue gas flows from left to right (forward        direction) while very cold N₂ gas flows from right to left        (reverse direction)] and (v) rapid collection of liquefied SO₂.    -   10. The methods of claims 1 & 2 and the use of equipment of        claim 3 comprising further steps to liquefy CO₂ (carbon dioxide)        contained in the said flue gas by adiabatically (isentropic)        compressing the remaining flue gas (after capture of SO₂ in        liquefied form in methods of claim 9) to a pressure of 26.47        bars, the said compression being achieved in successive stages        accompanied by necessary cooling to prevent the temperature rise        due to compressions and further cooling the compressed gas at        26.47 bars to a temperature of −10° C. or slightly below by        passing the said compressed flue gas through specialized tubes        contained in a special heat exchanger with chambers made for        rapid condensation of CO₂, collection of liquefied CO₂, and        rapid separation of flue gas from condensed CO₂ and for further        processing of the flue gas in later stages, the chambers being        cooled and maintained to required temperature (−16 to −20° C.)        to condense the compressed CO₂ of the flue gas to liquefied CO₂        (from the said pressurized flue gas at 26.47 bars) by passing        the said cold nitrogen gas in reverse directions from the point        of capture of nitrous oxide (N₂O) through the said heat        exchanger, similar to that in method of claim 9;    -   11. The methods of claims 1 & 2 and 10 further comprising steps        for (i) separation of the flue gas from liquefied CO₂ and speedy        collection of the said liquefied CO₂ that is steadily formed out        of the said flowing flue gas; (ii) for rapid production of dry        ice, using the whole or part of the collected liquefied CO₂        (temp ˜−10° C.), by throttling the latter adiabatically into an        enclosed (air tight) and well-insulated chamber (called flash        chamber here) inside of which being cooled to about 10 C below        −78° C. (the sublimation point of dry ice), by passing said very        cold nitrogen gas coming in reverse direction from the stage of        collection of liquid carbon monoxide from the flue gas and        thus (iii) freezing the dry CO₂ vapor (produced after the said        throttling of liquefied CO₂ from method (ii) of claim 11) into        dry ice along with freezing further the dry ice formed at the        first stage of throttling of said liquefied CO₂ by passing said        cold N₂ vapor into the flash chamber and (iv) including methods        of continuous separation and collection of the dry ice thus        formed in the specially built insulated flash chamber that uses        internal heat reflection and good external heat insulation;    -   12. The methods of claims 1 & 2 through the use of equipment of        claim 3 wherein capture of N₂O (nitrous oxide) from the        remaining part of the said flue gas (after separation of CO₂) is        accomplished by condensing nitrous oxide (N₂O) of the said flue        gas into liquid N₂O by: (i) first cooling the compressed flue        gas (at 26.4 bars and temperature around −10° C.) coming out        after liquefaction of CO₂ contained in the said flue gas in        methods of claim 11, to a temperature around −50° C. to −60° C.,        using said heat exchanger cooled by flow of part of the said        very cold nitrogen similar to that of method claim 10 and        then (ii) by first stage isentropic expansion of the compressed        and cold flue gas to about 13 to 15 bars, depending on the        initial temperature after the said cooling, by a first turbine        expander into a heat exchanger chamber cooled by the reverse        flow of said cold nitrogen gas (coming after capture of nitric        oxide by method of claim 13) to a temperature about 6 to 10° C.        below the boiling point (−88.5° C.) of nitrous oxide        (N₂O), (iii) by collecting the liquefied N₂O into an insulated        chamber attached to the heat exchanger, inner walls of which        have reflecting coatings and the outer walls well-insulated;    -   13. The methods of claims 1 to 2 through the use of equipment of        claim 3 wherein capture of nitric oxide (NO) from the remaining        part of the said flue gas (after capture of CO₂ and N₂O by        methods of claims 10-12) is accomplished by further cooling to        −106 to −110 ° C., of the said compressed flue gas remaining        after separation of CO₂ in methods of claims 11 & 12 and then        N₂O in methods of claim 12, followed by second stage isentropic        expansion of the compressed flue gas to about 4.87 bars to        condense the nitric oxide (NO) gas in the said flue gas to        liquefied NO (b.pt. −152° C. at atmospheric pressure) at        −152° C. or slightly above (as the pressure is higher than        atmospheric pressure) and capture of the liquefied NO into an        well-insulated container inside of which contains reflecting        walls and cooled to −156 to −160° C. by reverse flow of super        cold nitrogen gas produced after the capture of carbon monoxide        (CO) at the third stage turbine expansion in method of claim 14;    -   14. The methods of claims 1 to 2 with the use of equipment of        claim 3 where in methods of capturing carbon monoxide (b.pt.        −191.5° C. at atmospheric pressure) from the remaining part of        the said flue gas (after capturing NO in liquefied form using        method of claim 13) by further isentropic expansion (third        stage) of the said compressed flue gas (at temperature around        −152 ° C.) at pressure about 4.87 bars to atmospheric pressure        in order to further lower the temperature of the flue gas to        about 1 to 2 degrees above the boiling point of liquid nitrogen        (−196° C.) and rapid collection of the said carbon monoxide thus        condensed in specialized insulated chamber, so as to accomplish        separation of cold nitrogen gas from CO;    -   15. The methods of claims 1-2, 7-14 comprise of using        specialized heat exchanger chambers for capture of components        with boiling point above 0° C. and for capture of components        with boiling point below 0° C., with means of protection of said        heat exchanger tubes with specialized materials for prevention        against corrosion due to toxic components of flue gas through        use of any of the specialized materials of good thermal        conductivity, such as, but not limited to, vespel, torlon,        ryton, noryl or any other such suitable material that also        ensures tolerance of high initial temperature of the flue gas        and further ensures high thermal conduction between the hot said        flue gas passing through the turns of said tubes and the        surrounding cold temperatures of the said heat exchangers, as        required, for rapid cooling of the flue gas in different stages        in this invention, high heat radiation from the flue gas tubes        to the cold surroundings in the chambers, the said cold        temperature being produced by circulation of very cold nitrogen        gas obtained at the end of the cycle by methods of claim 14,        heat exchanges between the flue gas tubes and the cold nitrogen        gas flow tubes being further enhanced for temperatures below        0° C. through use of helium gas and metal chips or conducting        pebbles on perforated racks that surround the turns of separate        tubes carrying flue gas and the cold nitrogen gas;    -   16. The methods of claims 1 & 2 and 14 through the use of        equipment of claim 3 comprise of cooling the nitrogen gas        contained in the flue gas to temperature about 1 to 2 degrees        above the boiling point of liquid nitrogen at the third turbine        expansion of compressed flue gas and use of this super cooled        pure nitrogen gas through pumps in reverse directions and        splitting the cold nitrogen flow lines twice, firstly at (i) at        the point of feeding cold nitrogen gas to heat exchangers (a)        for NO liquefaction (b) for production of dry ice from liquefied        CO₂, secondly at (c) at the point of feeding the heat exchanger        for NO₂ liquefaction and (d) at the point of feeding the        condenser of ammonia power turbine, to perform required cooling        at various stages through the use of said heat exchangers for        capture of the individual components of pollutants, each        component separately from the incoming flue gas stream, without        use of any chemical/reagent, the said flue gas being from power        plants and industries, in general;    -   17. The methods of claims 1,2,3,5-11 require use of only fixed        amount of water and no chemical/reagent for capture of all or        any desired fraction CO₂ from the industrial flue gas and        production of large amount of liquefied CO₂ (source of highly        pure CO₂) and frozen dry ice (solid CO₂ at −78° C. or below,        which is also source of very pure CO₂) from the CO₂ gas        contained in the flue gas exiting from coal and natural gas        power plants and industries in general, the said fixed amount of        water being cooled in specialized chambers by cold nitrogen gas        obtained at the end of the cycle.    -   18. The technologies of claims 1,2, 4 to 15 provide means of        producing, after capturing CO₂ of the flue gas, liquefied CO₂        and dry ice (frozen CO₂) in entirety or in amount as needed,        together with means of capturing each of the associated        components such as, Hg, SO₃, NO₂, SO₂, N₂O, NO, CO, contained in        the flue gas emissions from coal and natural gas fired power        plants and industries in general, each of the components of SO₂,        CO₂, N₂O, NO, CO being captured separately without use of any        chemical/reagent except fixed amount of water, at the estimated        total energy cost (i) ($7.41 per ton of liquefied/frozen CO₂)        from the flue gas from coal fired power plants, when auxiliary        power is generated by ammonia turbine and $23.68 per ton of        liquefied or frozen CO₂, when auxiliary power is not generated,        assuming lkWh of electricity costs $0.12), (ii) at no energy        cost to the power plant, to capture entire emitted CO₂ and other        associated products if power is generated by using natural gas        when auxiliary power is generated as described in methods of        claim 4 and used for the said capture; and (iii) at $13.18 per        ton of the said cost that includes cost of capture (excluding        maintenance and labor) of all the said toxic components when        auxiliary power is not generated as described in this invention        or is not used for the said capture; (iv) the said capture costs        being lower than the lowest cost of any technique hitherto        available;    -   19. The methods of claims 1 & 2, 6 to 15, comprise of utilizing        the work generated during turbine expansion (at the final three        stages of the cycle) of compressed and cooled flue gas, for        partially aiding compression of the flue gas in successive        previous stages employing the n-stage compressors and thus to        increase energy efficiency of the whole capture process and to        reduce the energy cost of all the processes involved.    -   20. The methods of claim 1, 2, 3-15 wherein most cost effective        and energy efficient capture of each component of pollutants        contained in the emissions from power plants (using coal and        natural gas) and from industrial plants in general is        accomplished without use of any chemical/reagent and using only        fixed amount of water, depending on flue gas flow rate, its        temperature, after auxiliary power production through ammonia        turbine, such that the captured components SO₂ (liquid),        CO₂(liquid or solid), N₂O (liquid), NO(liquid), CO(liquid),        N₂(gas), each being highly pure (in the captured forms) can be        stored easily and find large industrial applications in the near        and distant future, where the entire capture is made possible at        a cost lower than the lowest cost of any technique hither to        available.

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Carbon Dioxide Separation from Flue Gases: A Technological ReviewEmphasizing Reduction in Greenhouse Gas Emissions

Mohammad Songolzadeh, Mansooreh Soleimani, Maryam Takht Ravanchi, andReza Songolzadeh

The Scientific World Journal, Volume 2014 (2014), Article ID 828131, 34pages http://dx.doi.org/10.1155/2014/828131

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We claim:
 1. A very cost effective and energy efficient technology ofcapturing industrial emissions (mercury (Hg) and its oxides, sulfurdioxide (SO₂), sulfur trioxide (SO₃), nitrogen dioxide (NO₂), carbondioxide (CO₂), nitrous oxide (N₂O), nitric oxide (NO), carbon monoxide(CO)) contained in the flue gas from coal and natural gas fired powerplants (all older and newer versions), cement plants and industrialplants in general, each component separately from each other and in theform of industrially useful product that can be conveniently stored, andthus to prevent or reduce/mitigate global warming/climatechange/environmental pollution/health effects arising due to suchgaseous emissions from the said industries into atmosphere & environmentand thus to ensure clean air/environment, using or requiring no chemicalreagent and no external cryogen, but only a small fraction of electricalpower from the output power of the plants or using the said neededelectrical power from any other source and fixed amount of water thatcan be repeatedly used during the capture process, comprising the stepsof : a) Generation of auxiliary electrical power using the heat of theflue gas using a turbine that can use anhydrous ammonia contained in anammonia super-heater, which is heated by the heat of the flue gas, theheat absorption of the said super heater being enhanced by coating onits surface a film of materials with high heat absorptivity and lowemissivity and its placement in an insulated chamber containing ceramicfilters to filter out the ashes & soot of the flue gas; b) passing theflue gas through ceramic filters, fabric filter, ESP (Electrostaticprecipitator), which capture partially the heat, the ashes,soot/floating particulates and partially the mercury and its oxides,with arrangement for removal of the ashes; c) reheating the ammoniaafter the turbine work by passing through the fabric filter & ESP inreverse direction; d) using successive compressions to specifiedpressures, successive cooling through use of specialized heat exchangersand successive adiabatic expansions of the said flue gas, throttling ofliquefied CO₂ when necessary; e) further cooling of the nitrogen (N₂)gas of the flue gas to a few (about 1 to 2) degrees above its boilingpoint (−196° C.) for using the said cold N₂ gas (by flowing it inreverse direction) to cool the flue gas at different steps, forindividual capture (separation) of the components; f) cooling in process1d) being accomplished by (i) passing adiabatically compressed flue gasthrough heat exchangers containing special tubes immersed in fixedamount of water, for capture of components with boiling points above 0°C., the water being cooled by flow of said cold nitrogen gas throughturns of tubes that surround the turns of tubes of the flue gas andradiative cooling arrangement, if the latter is needed; g) by passingadiabatically compressed flue gas, for individual capture of itscomponents with boiling points below 0° C., through heat exchangerscontaining (i) metal chips/or conducting pebbles on racks surroundingthe turns of tubes carrying said cold nitrogen gas which in turnsurrounds the turns of tubes carrying the said flue gas, all beingembedded in the chambers of the said heat exchangers and (ii) helium gasthat provides good heat conduction (exchange) between the flue gas tubesand the tubes carrying cold nitrogen gas and the pebbles/metal chips,which are cooled by the said cold nitrogen gas which has temperaturejust about 2 degree C. above its boiling point (−196° C.) producedthrough the third stage turbine expansion, following the step of captureof nitric oxide of the flue gas towards the end of a process cycle; h)superior control of cooling the flue gas to desired temperatures asrequired for capture of individual components of the flue gas, eachseparately through methods of claim 1f) & 1g), compared to heatexchanger chamber where cold nitrogen gas directly surrounds the saidturns of the flue gas tubes as the nitrogen gas directly enters throughthe inlet port and leaves through the outlet port of the chamber; i)repeating the compression, cooling (as in (ii) of 1e) and expansionsuccessively for 15 to 20 stages, or as necessary, depending on theinitial flue gas temperature and concentration of the components; j)fractionally liquefying or freezing each component of emissions atspecific temperature and pressure using the processes of claims 1a) to1i) for cooling the flue gas and using controlled amount of the saidsuper cooled nitrogen gas in successive stages of compression, coolingand expansion; k) using methods to control the temperatures of thechambers to specified temperatures by control of the very cold nitrogengas obtained by method of claim 1e) and through use of specialized heatexchangers of claim 1f) & 1g), standard temperature controller andstandard flow controller device; l) using methods of special coating toprevent corrosion of flow tubes, compressors, etc. due to corrosivecomponents of the flue gas and using flow tubes of special materials toensure very good thermal conduction of heat between hot flue gas and thecold nitrogen gas carrying flow tubes which are all embedded in the saidchambers of heat exchangers; m) utilizing the work generated duringturbine expansion (near the end of a cycle) of compressed N₂ for aidingcompression of flue gases in successive previous stages employing then-stage compressors and thus to increase energy efficiency of the wholecapture process;
 2. A method of capturing and production of liquefiedCO₂ and frozen CO₂ (dry ice), liquefied SO₂, liquefied SO₃, liquefiedNO₂, liquefied N₂O, liquefied NO, liquefied CO and pure nitrogen gas,each separately, from the flue gas of coal or natural gas powerplants/industrial plants in general, without use of anychemical/reagent, except fixed amount of water and a small amount ofenergy and with a single equipment, at operational cost far lower thanthat of any technology of industrial emission capture hitherto availableand at costs far lower than that of corresponding industrial productionsof the said components, each in fairly pure form that is industriallyusable;
 3. An equipment for very cost effective and energy efficientcapture of emission components from industrial flue gas, without usingany chemical/reagent and using fixed amount of water that is repeatedlyusable and for production of large amount of liquefied CO₂ and frozendry ice, which are sources of very pure CO₂, comprising a. chamberscontaining specially designed ceramic filters to remove fly ashesincluding oxides of mercury; b. fabric filters and electrostaticseparators to remove soot, smokes, any floating particles etc.; c.ammonia super heater with ammonia turbine for auxiliary power generationusing the heat of the flue gas with the surface of ammonia super heaterchamber been coated with films of high heat absorptivity and lowemissivity; d. pump & heat exchanger for the ammonia after turbineexpansion to capture some of the heat captured by the fabric filter &electro static separator from the flue gas, before the ammonia being fedto the ammonia super heater; e. heat exchangers with collecting chambersfor cooling and capturing components of flue gas (Hg, steam, SO₃, NO₂,acid vapors etc.) with boiling point above 0° C., with said heatexchangers containing water, which is cooled by passing cold nitrogengas, and using flue-gas flow tubes made of special materials that canstand temperature ˜300° C. and with high heat conductivity andnon-corrosive to the toxic components of the flue gas; f. heatexchangers for cooling and capturing components (SO₂, CO₂, N₂O, NO, CO)of flue gas with boiling point below 0° C. to specific temperatures atdifferent stages, the cooling being accomplished by passing very coldnitrogen gas (obtained at the end of a cycle of processing the flue gas)in reverse direction, through the turns of tubes that surround the turnsof tubes carrying flue gas, all being embedded in the said heatexchanger; g. the said heat exchangers (1f) containing conductingpebbles or metal chips arranged on racks surrounding the flue gas flowtubes and containing helium gas for superior heat conduction (forcapture of components with boiling point below 0° C.) between the fluegas in the flue gas flow tubes and the much colder surrounding obtainedby passing the said very cold nitrogen gas in reverse direction, throughthe turns of tubes that surround the turns of tubes carrying flue gas;h. flue gas-flow tubes and cold nitrogen gas flow tubes being made ofspecial materials that can tolerate temperatures up to 300° C. and lowtemperatures down to −194° C. and that have high thermal conductivity,the flue gas flow tube surfaces being painted black for superior heatradiation for faster cooling of flue gas; i. special chambers forcondensation of Hg, SO₃, NO₂ gases and collection of the correspondingliquids; j. compressors to compress flue gas at specific temperatures atdifferent stages to specific pressures and temperatures; k. specialchambers for condensation of CO₂ of flue gas and for rapid collectionsof liquefied CO₂ as needed; l. flash chambers for throttling ofliquefied CO₂ and arrangement of dry ice by passing very cold nitrogengas & rapid collection of dry ice CO₂; m. turbine expanders forexpansion of flue gas at specific pressures and temperatures; n. specialchambers for rapid condensation & collection of liquefied N₂O, NO andCO; o. split lines to inject cold nitrogen gas at different stages ofcapture of flue gas components, this being accomplished by reverse flowof cold nitrogen gas obtained after third turbine expansion at the endof the process cycle; p. cold nitrogen feedback lines and means of usingvery cold nitrogen gas for cooling the incoming flue gas throughappropriate heat exchangers; q. methods of good thermal insulation forthe split and feedback lines of super cold nitrogen gas; r. standardtemperature controller and pressure controller for nitrogen gas flow; 4.Methods of claims 1-2 through the use of equipment of claim 3 furthercomprising steps to extract the heat of the flue gas and convert it toauxiliary power, using (i) anhydrous ammonia super heater with coatingof films of high heat absorptivity and low emissivity material on itsexternal surface, the super heater being situated in the second chamberemployed for capture and removal of ash/mercury oxides from flue gas,(ii) raising the pressure of ammonia to around 200 bars and temperature200° C. (for efficiency around 20%) when the flue gas temperature isaround 500° C. or to around 100 bars and temperature 100° C. (forefficiency around 10%) when the flue gas temperature is dropped toaround 150° C. due to use of air pre-heating (APH); (iii) using turbinefor the auxiliary power generation (iv) heat exchanger processes thatalso condense partially, the mercury, the steam and the SO₃ (sulfurtrioxide) of the flue gas in specialized chamber (iv) pump to compressthe said turbine-expanded ammonia and to pass the compressed ammoniathrough a condenser to cool (using part of cold nitrogen gas diverted inreverse direction after capture of SO₂); (v) passing the condensedammonia through the said heat exchanger chamber and the chamber offabric filter/electrostatic precipitator to capture part of the flue gasheat trapped there and finally back to the ammonia super heater tocomplete the cycle, so that the auxiliary power is generated in cyclesto reduce the energy cost and to increase the energy efficiency of thecapture processes;
 5. The methods of claims 1 & 2 through the use ofequipment of claim 3 further include steps after reduction of flue gastemperature through method of claim 4, to condense partially mercuryvapor, steam, SO₃ (sulfur trioxide) including acid vapors of the fluegas, if any, in specialized chambers embedded in the said heat exchangerfollowing capture of ashes, mercury oxides etc;
 6. The methods of claims1 & 2 further comprising step to capture partial steam (H₂O), sulfurtrioxide and mercury of the flue gas by (i) further cooling totemperature less than 50° C. the flue gas remaining after method ofclaim 5 by passing the said flue gas through turns of tubes immersed inwater, which is cooled by passing said cold nitrogen gas throughseparate turns of tubes immersed in the said water; (ii) adiabaticcompression to 2 to 3 bars of the said flue gas from method of claim6(i) and further cooling of the compressed flue gas by passing throughspecial chamber containing turns of flue gas flow tubes immersed inwater, with water being cooled and maintained at 35±2° C. by controlledflow of the said cold nitrogen gas (method of 1e) through separate turnsof tubes immersed in the said water, the said flow being in a reversedirection looking from the step of the final capture of steam (H₂O),sulfur trioxide and mercury, as the said components (H₂O, SO₃ and Hg)condenses to respective liquids which are collected;
 7. The methods ofclaims 1 & 2 and the use of equipment of claim 3 further comprise of (i)steps to adiabatically compress the said flue gas after application ofmethod of claim 6 to pressure of 4.5 followed by (ii) cooling of thesaid compressed flue gas in specialized heat exchanger containing watercooled and maintained to required temperature (25±2° C.) by passingcontrolled flow of said cold nitrogen gas through turns of tubesimmersed in the water of the said heat exchanger, the flow being inreverse direction (after the NO₂ collection chamber seen from the rightin ways similar to that of methods of claims 6), for partial capture ofsteam (H₂O), final capture of sulfur trioxide and final capture ofmercury;
 8. The methods of claims 1 & 2 and the use of equipment 3wherein capture of NO₂ in the said flue gas in the form of liquid isaccomplished by (i) adiabatic compression of the said flue gas to 6 to 7bars pressure and (ii) by cooling to temperature ˜18 to 19° C. and (iii)collection of the liquefied NO₂;
 9. The methods of claims 1 and 2through the use of equipment of claim 3 further comprising steps of (i)adiabatic(isentropic) compression of flue gas remaining after capture ofnitrogen dioxide (NO₂), to a desired pressure (6 to 7 bars), (ii)cooling of the compressed said flue gas first to temperature 18±2° C.for condensation of NO₂, acid vapors like HNO₃, H₂SO₄ and part of steamin the flue gas and (iii) then cooling the said flue gas to temperaturearound 8° C.±2 for complete condensation of any remaining steam, NO₂,the said acid vapors of the flue gas to prevent chocking of thecompressors compressing the said flue gas below 0° C. in later stages,(iv) further compression of the flue gas remaining after completecondensation of steam to desired pressure (8 to 9 bars) (iv) passing thesaid adiabatically (isentropic) compressed gas through special heatexchangers where inside temperature is cooled to ˜−14° C. to −16° C.,for complete capture SO₂ of the flue gas in the form of liquid SO₂, therequired cooling being accomplished by passing in reverse direction thesaid cold N₂ gas coming from the point of capture of liquid CO₂ throughturns of tubes that surround the turns of tubes carrying the flue gas inseparate heat exchanger that does not contain water but conductingpebbles or metal chips on perforated racks that surround the said tubesand helium gas around 2 bars to improve heat exchange between the fluegas and the cold nitrogen gas and (v) rapid collection of liquefied SO₂.10. The methods of claims 1 & 2 and the use of equipment of claim 3comprising further steps to liquefy CO₂ (carbon dioxide) contained inthe said flue gas by adiabatically (isentropic) compressing theremaining flue gas (after capture of SO₂ in liquefied form in methods ofclaim 9) to a pressure of 26.47 bars, the said compression beingachieved in successive stages accompanied by necessary cooling toprevent the temperature rise due to compressions and further cooling thecompressed gas at 26.47 bars to a temperature of −10° C. or slightlybelow by passing the said compressed flue gas through specialized tubescontained in a special heat exchanger with chambers made for rapidcondensation of CO₂, collection of liquefied CO₂, and rapid separationof flue gas from condensed CO₂ and for further processing of the fluegas in later stages, the chambers being cooled and maintained torequired temperature (−16 to −20° C.) to condense the compressed CO₂ ofthe flue gas to liquefied CO₂ (from the said pressurized flue gas at26.47 bars) by passing the said cold nitrogen gas in reverse directionsfrom the point of capture of nitrous oxide (N₂O) through the said heatexchanger, similar to that in method of claim 9;
 11. The methods ofclaims 1 & 2 and 10 further comprising steps for (i) separation of theflue gas from liquefied CO₂ and speedy collection of the said liquefiedCO₂ that is steadily formed out of the said flowing flue gas; (ii) forrapid production of dry ice, using the whole or part of the collectedliquefied CO₂ (temp ˜−10° C.), by throttling the latter adiabaticallyinto an enclosed (air tight) and well-insulated chamber (called flashchamber here) inside of which being cooled to about 10 C below −78 ° C.(the sublimation point of dry ice), by passing said very cold nitrogengas coming in reverse direction from the stage of collection of liquidcarbon monoxide from the flue gas and thus (iii) freezing the dry CO₂vapor (produced after the said throttling of liquefied CO₂ from method(ii) of claim 11) into dry ice along with freezing further the dry iceformed at the first stage of throttling of said liquefied CO₂ by passingsaid cold N₂ vapor into the flash chamber and (iv) including methods ofcontinuous separation and collection of the dry ice thus formed in thespecially built insulated flash chamber that uses internal heatreflection and good external heat insulation;
 12. The methods of claims1 & 2 through the use of equipment of claim 3 wherein capture of N₂O(nitrous oxide) from the remaining part of the said flue gas (afterseparation of CO₂) is accomplished by condensing nitrous oxide (N₂O) ofthe said flue gas into liquid N₂O by: (i) first cooling the compressedflue gas (at 26.4 bars and temperature around −10° C.) coming out afterliquefaction of CO₂ contained in the said flue gas in methods of claim11, to a temperature around −50° C. to −60° C., using said heatexchanger cooled by flow of part of the said very cold nitrogen similarto that of method claim 10 and then (ii) by first stage isentropicexpansion of the compressed and cold flue gas to about 13 to 15 bars,depending on the initial temperature after the said cooling, by a firstturbine expander into a heat exchanger chamber cooled by the reverseflow of said cold nitrogen gas (coming after capture of nitric oxide bymethod of claim 13) to a temperature about 6 to 10° C. below the boilingpoint (−88.5° C.) of nitrous oxide (N₂O), (iii) by collecting theliquefied N₂O into an insulated chamber attached to the heat exchanger,inner walls of which have reflecting coatings and the outer wallswell-insulated;
 13. The methods of claims 1 to 2 through the use ofequipment of claim 3 wherein capture of nitric oxide (NO) from theremaining part of the said flue gas (after capture of CO₂ and N₂O bymethods of claims 10-12) is accomplished by further cooling to −106 to−110 ° C., of the said compressed flue gas remaining after separation ofCO₂ in methods of claims 11 & 12 and then N₂O in methods of claim 12,followed by second stage isentropic expansion of the compressed flue gasto about 4.87 bars to condense the nitric oxide (NO) gas in the saidflue gas to liquefied NO (b.pt. −152° C. at atmospheric pressure) at−152° C. or slightly above (as the pressure is higher than atmosphericpressure) and capture of the liquefied NO into an well-insulatedcontainer inside of which contains reflecting walls and cooled to −156to −160° C. by reverse flow of super cold nitrogen gas produced afterthe capture of carbon monoxide (CO) at the third stage turbine expansionin method of claim 14;
 14. The methods of claims 1 to 2 with the use ofequipment of claim 3 where in methods of capturing carbon monoxide(b.pt. −191.5° C. at atmospheric pressure) from the remaining part ofthe said flue gas (after capturing NO in liquefied form using method ofclaim 13) by further isentropic expansion (third stage) of the saidcompressed flue gas (at temperature around −152° C.) at pressure about4.87 bars to atmospheric pressure in order to further lower thetemperature of the flue gas to about 1 to 2 degrees above the boilingpoint of liquid nitrogen (−196° C.) and rapid collection of the saidcarbon monoxide thus condensed in specialized insulated chamber, so asto accomplish separation of cold nitrogen gas from CO;
 15. The methodsof claims 1-2, 7-14 comprise of using specialized heat exchangerchambers for capture of components with boiling point above 0° C. andfor capture of components with boiling point below 0° C., with means ofprotection of said heat exchanger tubes with specialized materials forprevention against corrosion due to toxic components of flue gas throughuse of any of the specialized materials of good thermal conductivity,such as, but not limited to, vespel, torlon, ryton, noryl or any othersuch suitable material that also ensures tolerance of high initialtemperature of the flue gas and further ensures high thermal conductionbetween the hot said flue gas passing through the turns of said tubesand the surrounding cold temperatures of the said heat exchangers, asrequired, for rapid cooling of the flue gas in different stages in thisinvention, high heat radiation from the flue gas tubes to the coldsurroundings in the chambers, the said cold temperature being producedby circulation of very cold nitrogen gas obtained at the end of thecycle by methods of claim 14, heat exchanges between the flue gas tubesand the cold nitrogen gas flow tubes being further enhanced fortemperatures below 0° C. through use of helium gas and metal chips orconducting pebbles on perforated racks that surround the turns ofseparate tubes carrying flue gas and the cold nitrogen gas;
 16. Themethods of claims 1 & 2 and 14 through the use of equipment of claim 3comprise of cooling the nitrogen gas contained in the flue gas totemperature about 1 to 2 degrees above the boiling point of liquidnitrogen at the third turbine expansion of compressed flue gas and useof this super cooled pure nitrogen gas through pumps in reversedirections and splitting the cold nitrogen flow lines twice, firstly at(i) at the point of feeding cold nitrogen gas to heat exchangers (a) forNO liquefaction (b) for production of dry ice from liquefied CO₂,secondly at (c) at the point of feeding the heat exchanger for NO₂liquefaction and (d) at the point of feeding the condenser of ammoniapower turbine, to perform required cooling at various stages through theuse of said heat exchangers for capture of the individual components ofpollutants, each component separately from the incoming flue gas stream,without use of any chemical/reagent, the said flue gas being from powerplants and industries, in general;
 17. The methods of claims 1,2,3,5-11require use of only fixed amount of water and no chemical/reagent forcapture of all or any desired fraction CO₂ from the industrial flue gasand production of large amount of liquefied CO₂ (source of highly pureCO₂) and frozen dry ice (solid CO₂ at −78° C. or below, which is alsosource of very pure CO₂) from the CO₂ gas contained in the flue gasexiting from coal and natural gas power plants and industries ingeneral, the said fixed amount of water being cooled in specializedchambers by cold nitrogen gas obtained at the end of the cycle.
 18. Thetechnologies of claims 1,2, 4 to 15 provide means of producing, aftercapturing CO₂ of the flue gas, liquefied CO₂ and dry ice (frozen CO₂) inentirety or in amount as needed, together with means of capturing eachof the associated components such as, Hg, SO₃, NO₂, SO₂, N₂O, NO, CO,contained in the flue gas emissions from coal and natural gas firedpower plants and industries in general, each of the components of SO₂,CO₂, N₂O, NO, CO being captured separately without use of anychemical/reagent except fixed amount of water, at the estimated totalenergy cost (i) ($7.41 per ton of liquefied/frozen CO₂) from the fluegas from coal fired power plants, when auxiliary power is generated byammonia turbine and $23.68 per ton of liquefied or frozen CO₂, whenauxiliary power is not generated, assuming lkWh of electricity costs$0.12), (ii) at no energy cost to the power plant, to capture entireemitted CO₂ and other associated products if power is generated by usingnatural gas when auxiliary power is generated as described in methods ofclaim 4 and used for the said capture; and (iii) at $13.18 per ton ofthe said cost that includes cost of capture (excluding maintenance andlabor) of all the said toxic components when auxiliary power is notgenerated as described in this invention or is not used for the saidcapture; (iv) the said capture costs being lower than the lowest cost ofany technique hitherto available;
 19. The methods of claims 1 & 2, 6 to15, comprise of utilizing the work generated during turbine expansion(at the final three stages of the cycle) of compressed and cooled fluegas, for partially aiding compression of the flue gas in successiveprevious stages employing the n-stage compressors and thus to increaseenergy efficiency of the whole capture process and to reduce the energycost of all the processes involved.
 20. The methods of claim 1,2, 3-15wherein most cost effective and energy efficient capture of eachcomponent of pollutants contained in the emissions from power plants(using coal and natural gas) and from industrial plants in general isaccomplished without use of any chemical/reagent and using only fixedamount of water, depending on flue gas flow rate, its temperature, afterauxiliary power production through ammonia turbine, such that thecaptured components SO₂ (liquid), CO₂ (liquid or solid), N₂O (liquid),NO (liquid), CO (liquid), N₂ (gas), each being highly pure (in thecaptured forms) can be stored easily and find large industrialapplications in the near and distant future, where the entire capture ismade possible at a cost lower than the lowest cost of any techniquehither to available.